Tempered glass sheet and method for manufacturing same

ABSTRACT

The present invention provides a tempered glass sheet having a compressive stress layer in a surface thereof, the tempered glass sheet including as a glass composition, in terms of mol %, 50% to 80% of SiO 2 , 8% to 25% of Al 2 O 3 , 0% to 10% of B 2 O 3 , 3% to 15% of Li 2 O, 3% to 21% of Na 2 O, 0% to 10% of K 2 O, 0% to 10% of MgO, 0% to 10% of ZnO, and 0% to 15% of P 2 O 5 .

TECHNICAL FIELD

The present invention relates to a tempered glass sheet and a method of manufacturing the same, and more particularly, to a tempered glass sheet suitable as a cover glass for a touch panel display of a cellular phone, a digital camera, a personal digital assistant (PDA), or the like, and a method of manufacturing the same.

BACKGROUND ART

In applications such as a cellular phone, a digital camera, and a personal digital assistant (PDA), a tempered glass sheet obtained through ion exchange treatment is used as a cover glass for a touch panel display (see Patent Literature 1 and Non Patent Literature 1).

CITATION LIST Patent Literature

-   Patent Literature 1: JP 2006-83045 A -   Patent Literature 2: JP 2016-524581 A -   Patent Literature 3: JP 2011-510903 A

Non Patent Literature

-   Non Patent Literature 1: Tetsuro Izumitani et al., “New glass and     physical properties thereof,” First edition, Management System     Laboratory. Co., Ltd., Aug. 20, 1984, p. 451-498

SUMMARY OF INVENTION Technical Problem

Incidentally, when a smartphone is dropped onto a road surface or the like by mistake, the smartphone becomes unusable in some cases owing to breakage of a cover glass. Accordingly, in order to avoid such situations, it is important to increase the strength of the tempered glass sheet.

As a method of increasing the strength of the tempered glass sheet, it is effective to increase a depth of layer. Specifically, when the cover glass collides with the road surface at the time of dropping of the smartphone, protrusions or sand grains on the road surface penetrate into the cover glass to reach a tensile stress layer, which leads to the breakage of the cover glass. In view of the foregoing, when the depth of layer of a compressive stress layer is increased, the protrusions or the sand grains on the road surface are less liable to reach the tensile stress layer, and thus the breakage probability of the cover glass can be reduced.

Lithium aluminosilicate glass is advantageous in obtaining a large depth of layer. In particular, when a glass sheet to be tempered, which is formed of the lithium aluminosilicate glass, is immersed in a molten salt containing NaNO₃ to ion exchange a Li ion in the glass with a Na ion in the molten salt, a tempered glass sheet having a large depth of layer can be obtained.

However, with related-art lithium aluminosilicate glass, there is a risk in that the compressive stress value of the compressive stress layer may be reduced excessively. Meanwhile, when a glass composition is designed so as to increase the compressive stress value of the compressive stress layer, there is a risk in that chemical stability may be reduced. Further, it is difficult to form the lithium aluminosilicate glass into a sheet shape because devitrified stones are liable to be generated at the time of forming owing to an unbalanced glass composition.

The present invention has been made in view of the above-mentioned circumstances, and a technical object of the present invention is to provide a tempered glass sheet, which can be formed into a sheet shape, is excellent in chemical stability, and is less liable to be broken at the time of dropping.

Solution to Problem

The inventors of the present invention have made various investigations, and as a result, have found that, when the glass composition is restricted to a predetermined range, the above-mentioned technical object can be achieved. Thus, the finding is proposed as the present invention. That is, according to one embodiment of the present invention, there is provided a tempered glass sheet having a compressive stress layer in a surface thereof, the tempered glass sheet comprising as a glass composition, in terms of mol %, 50% to 80% of SiO₂, 8% to 25% of Al₂O₃, 0% to 10% of B₂O₃, 3% to 15% of Li₂O, 3% to 21% of Na₂O, 0% to 10% of K₂O, 0% to 10% of MgO, 0% to 10% of ZnO, and 0% to 15% of P₂O₅.

In addition, it is preferred that the tempered glass sheet according to the one embodiment of the present invention satisfy the following relationship: a molar ratio ([Na₂O]−[Li₂O])/([Al₂O₃]+[B₂O₃]+[P₂O₅])≤0.29. Herein, the “[Na₂O]” refers to the content of Na₂O in terms of mol %. The “[Li₂O]” refers to the content of Li₂O in terms of mol %. The “[Al₂O₃]” refers to the content of Al₂O₃ in terms of mol %. The “[B₂O₃]” refers to the content of B₂O₃ in terms of mol %. The “[P₂O₅]” refers to the content of P₂O₅ in terms of mol %. The “([Na₂O]−[Li₂O])/([Al₂O₃]+[B₂O₃]+[P₂O₅])” refers to a value obtained by dividing a value obtained by subtracting the content of Li₂O from the content of Na₂O by the total content of Al₂O₃, B₂O₃, and P₂O₅.

In addition, it is preferred that the tempered glass sheet according to the one embodiment of the present invention satisfy the following relationship: a molar ratio ([B₂O₃]+[Na₂O]− [P₂O₅])/([Al₂O₃]+[Li₂O])≥0.30. Herein, the “([B₂O₃]+[Na₂O]−[P₂O₅])/([Al₂O₃]+[Li₂O])” refers to a value obtained by dividing a value obtained by subtracting the content of P₂O₅ from the total content of B₂O₃ and Na₂O by the total content of Al₂O₃ and Li₂O.

In addition, the tempered glass sheet according to the one embodiment of the present invention comprises 12 mol % or more of ([Li₂O]+[Na₂O]+[K₂O]), and satisfies the following relationship: [SiO₂]+1.2×[P₂O₅]−3×[Al₂O₃]−2×[Li₂O]−1.5×[Na₂O]−[K₂O]−[B₂O₃]≥−22 mol %. Herein, the “[K₂O]” refers to the content of K₂O in terms of mol %. The “[SiO₂]” refers to the content of SiO₂ in terms of mol %. The “([Li₂O]+[Na₂O]+[K₂O])” refers to the total content of Li₂O, Na₂O, and K₂O. The “[SiO₂]+1.2×[P₂O₅]−3×[Al₂O₃]−2×[Li₂O]−1.5×[Na₂O]−[K₂O]−[B₂O₃]” refers to a value obtained by subtracting a content three times as large as the content of Al₂O₃, a content two times as large as the content of Li₂O, a content 1.5 times as large as the content of Na₂O, the content of K₂O, and the content of B₂O₃ from the sum of the content of SiO₂ and a content 1.2 times as large as the content of P₂O₅.

In addition, it is preferred that the tempered glass sheet according to the one embodiment of the present invention have a content of P₂O₅ of from 0.1 mol % to 2.3 mol %.

In addition, it is preferred that the tempered glass sheet according to the one embodiment of the present invention have a content of B₂O₃ of from 0.1 mol % to 4 mol %.

In addition, it is preferred that, in the tempered glass sheet according to the one embodiment of the present invention, the compressive stress layer have a compressive stress value of from 200 MPa to 1,000 MPa on an outermost surface. Herein, the “compressive stress value on the outermost surface” and the “depth of layer” each refer to a value measured based on a retardation distribution curve observed, for example, with a scattered light photoelastic stress meter SLP-1000 (manufactured by Orihara Industrial Co., Ltd.). Moreover, the “depth of layer” refers to a depth at which the stress value becomes zero. In calculation of the stress characteristics, the refractive index and the optical elastic constant of each measurement sample are set to 1.51 and 30.1 [(nm/cm)/MPa], respectively.

In addition, it is preferred that, in the tempered glass sheet according to the one embodiment of the present invention, the compressive stress layer have a depth of layer of from 50 μm to 200 μm.

In addition, it is preferred that the tempered glass sheet according to the one embodiment of the present invention have a temperature at a viscosity at high temperature of 10^(2.5) dPa·s of less than 1,650° C. Herein, the “temperature at a viscosity at high temperature of 10^(2.5) dPa·s” may be measured, for example, by a platinum sphere pull up method.

In addition, it is preferred that the tempered glass sheet according to the one embodiment of the present invention comprise overflow-merged surfaces in a middle portion thereof in a sheet thickness direction, that is, the tempered glass sheet be formed by an overflow down-draw method. Herein, the “overflow down-draw method” is a method involving causing molten glass to overflow from both sides of forming body refractory, and subjecting the overflowing molten glasses to down-draw downward while the molten glasses are merged at the lower end of the forming body refractory, to thereby manufacture a glass sheet.

In addition, it is preferred that the tempered glass sheet according to the one embodiment of the present invention be used as a cover glass for a touch panel display.

In addition, the tempered glass sheet according to the one embodiment of the present invention is a tempered glass sheet having a compressive stress layer in a surface thereof, the tempered glass sheet comprising, as the glass composition, 17 mol % or more of Al₂O₃, 1 mol % or more of P₂O₅, and 12 mol % or more of ([Li₂O]+[Na₂O]+[K₂O]), and satisfying the following relationship: [SiO₂]+1.2×[P₂O₅]−3×[Al₂O₃]−2×[Li₂O]−1.5×[Na₂O]−[K₂O]−[B₂O₃]≥−22 mol %. With this configuration, glass that can be formed into a sheet shape and further has high acid resistance while being increased in ion exchange performance becomes easily obtainable.

In addition, it is preferred that the tempered glass sheet according to the one embodiment of the present invention have a content of Fe₂O₃ of from 0.001 mol % to 0.1 mol %.

In addition, it is preferred that the tempered glass sheet according to the one embodiment of the present invention have a content of TiO₂ of from 0.001 mol % to 0.1 mol %.

In addition, it is preferred that the tempered glass sheet according to the one embodiment of the present invention have a content of SnO₂ of from 0.01 mol % to 1 mol %.

In addition, it is preferred that the tempered glass sheet according to the one embodiment of the present invention have a content of Cl of from 0.001 mol % to 0.1 mol %.

In addition, it is preferred that the tempered glass sheet according to the one embodiment of the present invention have a stress profile having at least a first peak, a second peak, a first bottom, and a second bottom in a thickness direction.

According to one embodiment of the present invention, there is provided a glass sheet to be tempered, comprising as a glass composition, in terms of mol %, 50% to 80% of SiO₂, 8% to 25% of Al₂O₃, 0% to 10% of B₂O₃, 3% to 15% of Li₂O, 3% to 21% of Na₂O, 0% to 10% of K₂O, 0% to 10% of MgO, 0% to 10% of ZnO, and 0% to 15% of P₂O₅.

According to one embodiment of the present invention, there is provided a method of manufacturing a tempered glass sheet, comprising: a preparation step of preparing a glass sheet to be tempered including as a glass composition, in terms of mol %, 50% to 80% of SiO₂, 8% to 25% of Al₂O₃, 0% to 10% of B₂O₃, 3% to 15% of Li₂O, 3% to 21% of Na₂O, 0% to 10% of K₂O, 0% to 10% of MgO, 0% to 10% of ZnO, and 0% to 15% of P₂O₅; and anion exchange step of subjecting the glass sheet to be tempered to ion exchange treatment a plurality of times, to thereby obtain a tempered glass sheet having a compressive stress layer in a surface thereof.

BRIEF DESCRIPTION OF DRAWINGS

FIG. 1 is an explanatory view for illustrating an example of a stress profile having a first peak, a second peak, a first bottom, and a second bottom.

FIG. 2 is another explanatory view for illustrating an example of a stress profile having a first peak, a second peak, a first bottom, and a second bottom.

DESCRIPTION OF EMBODIMENTS

A tempered glass sheet (glass sheet to be tempered) of the present invention comprises as a glass composition, in terms of mol %, 50% to 80% of SiO₂, 8% to 25% of Al₂O₃, 0% to 10% of B₂O₃, 3% to 15% of Li₂O, 3% to 21% of Na₂O, 0% to 10% of K₂O, 0% to 10% of MgO, 0% to 10% of ZnO, and 0% to 15% of P₂O₅. Reasons why the content ranges of the components are restricted are described below. In the description of the content range of each component, the expression “%” means “mol %” unless otherwise specified.

SiO₂ is a component that forms a glass network. When the content of SiO₂ is too small, vitrification does not occur easily, and a thermal expansion coefficient becomes too high, with the result that thermal shock resistance is liable to be reduced. Accordingly, a suitable lower limit of the content range of SiO₂ is 50% or more, 55% or more, 57% or more, or 59% or more, particularly 61% or more. Meanwhile, when the content of SiO₂ is too large, meltability and formability are liable to be reduced, and the thermal expansion coefficient is excessively reduced, with the result that it becomes difficult to match the thermal expansion coefficient with those of peripheral materials. Accordingly, a suitable upper limit of the content range of SiO₂ is 80% or less, 70% or less, 68% or less, 66% or less, or 65% or less, particularly 64.5% or less.

Al₂O₃ is a component that improves ion exchange performance, and is also a component that increases a strain point, a Young's modulus, a fracture toughness, and a Vickers hardness. Accordingly, a suitable lower limit of the content range of Al₂O₃ is 8% or more, 10% or more, 12% or more, 13% or more, 14% or more, 14.4% or more, 15% or more, 15.3% or more, 15.6% or more, 16% or more, 16.5% or more, 17% or more, 17.2% or more, 17.5% or more, 17.8% or more, 18% or more, more than 18%, or 18.3% or more, particularly 18.5% or more, 18.6% or more, 18.7% or more, or 18.8% or more. Meanwhile, when the content of Al₂O₃ is too large, a viscosity at high temperature is increased, with the result that the meltability and the formability are liable to be reduced. In addition, a devitrified crystal is liable to be precipitated in the glass, and it becomes difficult to form the glass into a sheet shape by an overflow down-draw method or the like. Particularly when the glass is formed into a sheet shape by an overflow down-draw method involving using alumina-based refractory as forming body refractory, a devitrified crystal of spinel is liable to be precipitated at an interface with the alumina-based refractory. Further, acid resistance is reduced, with the result that it becomes difficult to subject the glass to an acid treatment step. Accordingly, a suitable upper limit of the content range of Al₂O₃ is 25% or less, 21% or less, 20.5% or less, 20% or less, 19.9% or less, 19.5% or less, or 19.0% or less, particularly 18.9% or less. When the content of Al₂O₃, which has a large influence on the ion exchange performance, is set to fall with the suitable ranges, a profile having a first peak, a second peak, a first bottom, and a second bottom becomes easily formable.

B₂O₃ is a component that reduces the viscosity at high temperature and a density, and stabilizes the glass to cause less precipitation of a crystal, to thereby reduce a liquidus temperature. When the content of B₂O₃ is too small, a depth of layer obtained through ion exchange between a Li ion in the glass and a Na ion in a molten salt is excessively increased, with the result that the compressive stress value (CS_(Na)) of a compressive stress layer is liable to be reduced. In addition, there is a risk in that the glass may be unstable, and devitrification resistance may be reduced. Accordingly, a suitable lower limit of the content range of B₂O₃ is 0% or more, 0.1% or more, 0.2% or more, 0.5% or more, 0.6% or more, 0.7% or more, 0.8% or more, or 0.9% or more, particularly 1% or more. Meanwhile, when the content of B₂O₃ is too large, there is a risk in that the depth of layer may be reduced. In particular, the efficiency of ion exchange between a Na ion in the glass and a K ion in a molten salt is liable to be reduced, and the depth of layer (DOL_ZERO_(K)) of the compressive stress layer is liable to be reduced. Accordingly, a suitable upper limit of the content range of B₂O₃ is 10% or less, 5% or less, 4% or less, 3.8% or less, 3.5% or less, 3.3% or less, 3.2% or less, 3.1% or less, or 3% or less, particularly 2.9% or less. When the content of B₂O₃ is set to fall within the suitable ranges, the profile having a first peak, a second peak, a first bottom, and a second bottom becomes easily formable.

Li₂O is an ion exchange component, and particularly, is an essential component for obtaining a large depth of layer through ion exchange between a Li ion in the glass and a Na ion in the molten salt. In addition, Li₂O is a component that reduces the viscosity at high temperature to improve the meltability and the formability, and is also a component that increases the Young's modulus. Accordingly, a suitable lower limit of the content range of Li₂O is 3% or more, 4% or more, 5% or more, 5.5% or more, 6.5% or more, 7% or more, 7.3% or more, 7.5% or more, or 7.8% or more, particularly 8% or more. Accordingly, a suitable upper limit of the content range of Li₂O is 15% or less, 13% or less, 12% or less, 11.5% or less, 11% or less, 10.5% or less, or less than 10%, particularly 9.9% or less, 9% or less, or 8.9% or less.

Na₂O is an ion exchange component, and is also a component that reduces the viscosity at high temperature to improve the meltability and the formability. In addition, Na₂O is a component that improves the devitrification resistance, and is particularly a component that suppresses devitrification caused by a reaction with alumina-based refractory. Accordingly, a suitable lower limit of the content range of Na₂O is 3% or more, 4% or more, 5% or more, 6% or more, 7% or more, 7.5% or more, 8% or more, 8.5% or more, or 8.8% or more, particularly 9% or more. Meanwhile, when the content of Na₂O is too large, the thermal expansion coefficient is excessively increased, and the thermal shock resistance is liable to be reduced. In addition, the glass composition loses its component balance, and the devitrification resistance may be reduced contrarily. Accordingly, a suitable upper limit of the content range of Na₂O is 21% or less, 20% or less, or 19% or less, particularly 18% or less, 15% or less, 13% or less, or 11% or less, particularly 10% or less.

K₂O is a component that reduces the viscosity at high temperature to improve the meltability and the formability. However, when the content of K₂O is too large, the thermal expansion coefficient is excessively increased, and the thermal shock resistance is liable to be reduced. In addition, the compressive stress value of the compressive stress layer on the outermost surface is liable to be reduced. Accordingly, a suitable upper limit of the content range of K₂O is 10% or less, 7% or less, 6% or less, 5% or less, 4% or less, 3% or less, 2% or less, 1.5% or less, 1% or less, less than 1%, or 0.5% or less, particularly less than 0.1%. When the viewpoint of increasing the depth of layer is emphasized, a suitable lower limit of the content range of K₂O is 0% or more, 0.1% or more, or 0.3% or more, particularly 0.5% or more.

The molar ratio [Li₂O]/([Na₂O]+[K₂O]) is preferably from 0.4 to 1.0, or from 0.5 to 0.9, particularly preferably from 0.6 to 0.8. When the molar ratio [Li₂O]/([Na₂O]+[K₂O]) is too low, there is a risk in that the ion exchange performance cannot be sufficiently exhibited. In particular, the efficiency of ion exchange between a Li ion in the glass and a Na ion in the molten salt is liable to be reduced. Meanwhile, when the molar ratio [Li₂O]/([Na₂O]+[K₂O]) is too high, a devitrified crystal is liable to precipitate in the glass, and it becomes difficult to form the glass into a sheet shape by an overflow down-draw method or the like. The “[Li₂O]/([Na₂O]+[K₂O])” refers to a value obtained by dividing the content of Li₂O by the total content of Na₂O and K₂O.

MgO is a component that reduces the viscosity at high temperature to improve the meltability and the formability, and increases the strain point and the Vickers hardness. Among alkaline earth metal oxides, MgO is a component that has a high effect of improving the ion exchange performance. However, when the content of MgO is too large, the devitrification resistance is liable to be reduced, and particularly, it becomes difficult to suppress devitrification caused by a reaction with alumina-based refractory. Accordingly, a suitable content of MgO is from 0% to 10%, from 0% to 5%, from 0.1% to 4%, or from 0.2% to 3.5%, particularly from 0.5% to less than 3%.

ZnO is a component that improves the ion exchange performance, and particularly, is a component that has a high effect of increasing the compressive stress value of the compressive stress layer on the outermost surface. In addition, ZnO is also a component that reduces the viscosity at high temperature without reducing a viscosity at low temperature. A suitable lower limit of the content range of ZnO is 0% or more, 0.1% or more, 0.3% or more, 0.5% or more, or 0.7% or more, particularly 1% or more. Meanwhile, when the content of ZnO is too large, there is a tendency that the glass undergoes phase separation, the devitrification resistance is reduced, the density is increased, or the depth of layer is reduced. Accordingly, a suitable upper limit of the content range of ZnO is 10% or less, 6% or less, 5% or less, 4% or less, 3% or less, 2% or less, 1.5% or less, 1.3% or less, or 1.2% or less, particularly 1.1% or less.

P₂O₅ is a component that improves the ion exchange performance, and particularly, is a component that increases the depth of layer. Further, P₂O₅ is a component that also improves the acid resistance. When the content of P₂O₅ is too small, there is a risk in that the ion exchange performance cannot be sufficiently exhibited. In particular, the efficiency of ion exchange between a Na ion in the glass and a K ion in the molten salt is liable to be reduced, and the depth of layer (DOL_ZERO_(K)) of the compressive stress layer is liable to be reduced. In addition, there is a risk in that the glass may be unstable, and the devitrification resistance may be reduced. Accordingly, a suitable lower limit of the content range of P₂O₅ is 0% or more, 0.1% or more, 0.4% or more, 0.7% or more, 1% or more, 1.2% or more, 1.4% or more, 1.6% or more, 2% or more, 2.3% or more, or 2.5% or more, particularly 3% or more. Meanwhile, when the content of P₂O₅ is too large, the glass undergoes phase separation, or water resistance is liable to be reduced. In addition, the depth of layer obtained through ion exchange between a Li ion in the glass and a Na ion in the molten salt is excessively increased, with the result that the compressive stress value (CS_(Na)) of the compressive stress layer is liable to be reduced. Accordingly, a suitable upper limit of the content range of P₂O₅ is 15% or less, 10% or less, 5% or less, 4.5% or less, or 4% or less. When the content of P₂O₅ is set to fall within the suitable ranges, a non-monotonic profile becomes easily formable.

An alkali metal oxide is an ion exchange component, and is also a component that reduces the viscosity at high temperature to improve the meltability and the formability. When the content of the alkali metal oxide ([Li₂O]+[Na₂O]+[K₂O]) is too large, there is a risk in that the thermal expansion coefficient may be increased. In addition, there is a risk in that the acid resistance may be reduced. Accordingly, a suitable lower limit of the content range of the alkali metal oxide ([Li₂O]+[Na₂O]+[K₂O]) is 10% or more, 11% or more, 12% or more, 13% or more, 14% or more, or 15% or more. Accordingly, a suitable upper limit of the content range of the alkali metal oxide ([Li₂O]+[Na₂O]+[K₂O]) is 25% or less, 23% or less, 20% or less, 19% or less, or 18% or less.

The molar ratio [Li₂O]/[P₂O₅] is preferably from 4 to 30, or from 10 to 25, particularly preferably from 15 to 20. When the molar ratio [Li₂O]/[P₂O₅] is too low, the efficiency of ion exchange between a Li ion in the glass and a Na ion in the molten salt is liable to be reduced. Meanwhile, when the molar ratio [Li₂O]/[P₂O₅] is too high, a devitrified crystal is liable to precipitate in the glass, and it becomes difficult to form the glass into a sheet shape by an overflow down-draw method or the like. The “[Li₂O]/[P₂O₅]” refers to a value obtained by dividing the content of Li₂O by the content of P₂O₅.

The molar ratio ([Na₂O]−[Li₂O])/([Al₂O₃]+[B₂O₃]+[P₂O₅]) is preferably 0.29 or less, 0.27 or less, 0.26 or less, 0.25 or less, 0.23 or less, or 0.20 or less, particularly preferably 0.00 or more and 0.15 or less. When the molar ratio ([Na₂O]−[Li₂O])/([Al₂O₃]+[B₂O₃]+[P₂O₅]) is too high, there is a risk in that the ion exchange performance cannot be sufficiently exhibited. In particular, the efficiency of ion exchange between a Li ion in the glass and a Na ion in the molten salt is liable to be reduced.

The molar ratio ([B₂O₃]+[Na₂O]−[P₂O₅])/([Al₂O₃]+[Li₂O]) is preferably 0.30 or more, 0.35 or more, 0.40 or more, 0.42 or more, or 0.43 or more, particularly preferably 0.45 or more and 1.24 or less. When the molar ratio ([B₂O₃]+[Na₂O]−[P₂O₅])/([Al₂O₃]+[Li₂O]) is too low, a devitrified crystal is liable to precipitate in the glass, and it becomes difficult to form the glass into a sheet shape by an overflow down-draw method or the like.

The ([SiO₂]+1.2×[P₂O₅]−3×[Al₂O₃]−2×[Li₂O]−1.5×[Na₂O]−[K₂O]−[B₂O₃]) is preferably −40% or more, −30% or more, −25% or more, −24% or more, −23% or more, −22% or more, −21% or more, −20% or more, or −19% or more, particularly preferably −18% or more. When the ([SiO₂]+1.2×[P₂O₅]−3×[Al₂O₃]−2×[Li₂O]−1.5×[Na₂O]−[K₂O]−[B₂O₃]) is too low, the acid resistance is liable to be reduced. Meanwhile, when the ([SiO₂]+1.2×[P₂O₅]−3×[Al₂O₃]−2×[Li₂O]−1.5×[Na₂O]−[K₂O]−[B₂O₃]) is too high, there is a risk in that the ion exchange performance cannot be sufficiently exhibited. Accordingly, the ([SiO₂]+1.2×[P₂O₅]−3×[Al₂O₃]−2×[Li₂O]−1.5×[Na₂O]−[K₂O]−[B₂O₃]) is preferably 30 mol % or less, 20 mol % or less, 15 mol % or less, 10 mol % or less, or 5 mol % or less, particularly preferably 0 mol % or less.

For example, the following components other than the above-mentioned components may be added.

CaO is a component that reduces the viscosity at high temperature to improve the meltability and the formability without reducing the devitrification resistance as compared to other components, and increases the strain point and the Vickers hardness. However, when the content of CaO is too large, there is a risk in that the ion exchange performance may be reduced, or an ion exchange solution may be degraded at the time of ion exchange treatment. Accordingly, a suitable upper limit of the content range of CaO is 6% or less, 5% or less, 4% or less, 3.5% or less, 3% or less, 2% or less, 1% or less, less than 1%, or 0.5% or less, particularly less than 0.1%.

SrO and BaO are each a component that reduces the viscosity at high temperature to improve the meltability and the formability, and increases the strain point and the Young's modulus. However, when the contents of SrO and BaO are too large, an ion exchange reaction is liable to be inhibited. Besides, the density or the thermal expansion coefficient is increased inappropriately, or the glass is liable to devitrify. Accordingly, suitable contents of SrO and BaO are each from 0% to 2%, from 0% to 1.5%, from 0% to 1%, from 0% to 0.5%, or from 0% to 0.1%, particularly from 0% to less than 0.1%.

ZrO₂ is a component that increases the Vickers hardness, and is also a component that increases viscosity around the liquidus viscosity and the strain point. However, when the content of ZrO₂ is too large, there is a risk in that the devitrification resistance is remarkably reduced. Accordingly, a suitable content of ZrO₂ is from 0% to 3%, from 0% to 1.5%, or from 0% to 1%, particularly from 0% to 0.1%.

TiO₂ is a component that improves the ion exchange performance, and is also a component that reduces the viscosity at high temperature. However, when the content of TiO₂ is too large, transparency and the devitrification resistance are liable to be reduced. Accordingly, a suitable content of TiO₂ is from 0% to 3%, from 0% to 1.5%, from 0% to 1%, or from 0% to 0.1%, particularly from 0.001 mol % to 0.1 mol %.

SnO₂ is a component that improves the ion exchange performance. However, when the content of SnO₂ is too large, the devitrification resistance is liable to be reduced. Accordingly, a suitable lower limit of the content range of SnO₂ is 0.005% or more, or 0.01% or more, particularly 0.1% or more, and a suitable upper limit thereof is 3% or less, or 2% or less, particularly 1% or less.

Cl is a fining agent, but is a component that adversely affects an environment or a facility when the content thereof is too large. Accordingly, a suitable lower limit of the content range of Cl is 0.001% or more, particularly 0.01% or more, and a suitable upper limit thereof is 0.3% or less, or 0.2% or less, particularly 0.1% or less.

As a fining agent, one kind or two or more kinds selected from the group consisting of SO₃ and CeO₂ (preferably the group consisting of SO₃) may be added at from 0.001% to 1%.

Fe₂O₃ is an impurity that is inevitably mixed in from raw materials. A suitable content of Fe₂O₃ is less than 1,000 ppm (less than 0.1%), less than 800 ppm, less than 600 ppm, or less than 400 ppm, particularly less than 300 ppm. When the content of Fe₂O₃ is too large, the transmittance of a cover glass is liable to be reduced.

Meanwhile, the lower limit of the content range of Fe₂O₃ is 10 ppm or more, 20 ppm or more, 30 ppm or more, 50 ppm or more, 80 ppm or more, or 100 ppm or more. When the content of Fe₂O₃ is too small, a raw material cost rises owing to the use of high-purity raw materials, and a product cannot be manufactured inexpensively.

A rare earth oxide, such as Nd₂O₃, La₂O₃, Y₂O₃, Nb₂O₅, Ta₂O₅, or Hf₂O₃, is a component that increases the Young's modulus. However, the costs of raw materials therefor are high. In addition, when the rare earth oxide is added in a large amount, the devitrification resistance is liable to be reduced. Accordingly, a suitable content of the rare earth oxide is 5% or less, 3% or less, 2% or less, 1% or less, or 0.5% or less, particularly 0.1% or less.

It is preferred that the tempered glass sheet (glass sheet to be tempered) of the present invention be substantially free of As₂O₃, Sb₂O₃, PbO, and F as a glass composition from the standpoint of environmental considerations. In addition, it is also preferred that the tempered glass sheet (glass sheet to be tempered) be substantially free of Bi₂O₃ from the standpoint of environmental considerations. The “substantially free of” has a concept in which the explicit component is not positively added as a glass component, but its addition at an impurity level is permitted, and specifically refers to the case in which the content of the explicit component is less than 0.05%.

The tempered glass sheet (glass sheet to be tempered) of the present invention preferably has the following characteristics.

A density is preferably 2.55 g/cm³ or less, 2.53 g/cm³ or less, 2.50 g/cm³ or less, 2.49 g/cm³ or less, or 2.45 g/cm³ or less, particularly preferably from 2.35 g/cm³ to 2.44 g/cm³. As the density becomes lower, the weight of the tempered glass sheet can be reduced more.

A thermal expansion coefficient at from 30° C. to 380° C. is preferably 150×10⁻⁷/° C. or less, or 100×10⁻⁷/° C. or less, particularly preferably from 50×10⁻⁷/° C. to 95×10⁻⁷/° C. The “thermal expansion coefficient at from 30° C. to 380° C.” refers to a value for an average thermal expansion coefficient measured with a dilatometer.

A softening point is preferably 950° C. or less, 930° C. or less, 900° C. or less, 880° C. or less, or 860° C. or less, particularly preferably from 850° C. to 700° C. The “softening point” refers to a value measured based on a method of ASTM C338.

A temperature at a viscosity at high temperature of 10^(2.5) dPa·s is preferably 1,660° C. or less, less than 1,620° C., or 1,600° C. or less, particularly preferably from 1,400° C. to 1,590° C. When the temperature at a viscosity at high temperature of 10^(2.5) dPa·s is too high, the meltability and the formability are reduced, with the result that it becomes difficult to form molten glass into a sheet shape. The “temperature at a viscosity at high temperature of 10^(2.5) dPa·s” refers to a value measured by a platinum sphere pull up method.

A liquidus viscosity is preferably 10^(3.74) dPa·s or more, 10^(4.5) dPa·s or more, 10^(4.8) dPa·s or more, 10^(4.9) dPa·s or more, 10^(5.0) dPa·s or more, 10^(5.1) dPa·s or more, 10^(5.2) dPa·s or more, 10^(5.3) dPa·s or more, or 10^(5.4) dPa·s or more, particularly preferably 10^(5.5) dPa·s or more. As the liquidus viscosity becomes higher, devitrification resistance is improved more, and devitrified stones are less liable to be generated at the time of forming. The “liquidus viscosity” as used herein refers to a value for a viscosity at a liquidus temperature measured by a platinum sphere pull up method. The “liquidus temperature” refers to a temperature obtained as described below. Glass powder which has passed through a standard 30-mesh sieve (500 μm) and remained on a 50-mesh sieve (300 μm) is loaded into a platinum boat, and the platinum boat is kept for 24 hours in a temperature gradient furnace and is then taken out of the furnace. At this time, a highest temperature at which devitrification (devitrified stones) is observed with a microscope in glass is measured.

A Young's modulus is preferably 70 GPa or more, 74 GPa or more, or from 75 GPa to 100 GPa, particularly preferably from 76 GPa to 90 GPa. When the Young's modulus is small, the cover glass is liable to be deflected in the case of having a small thickness. The “Young's modulus” may be calculated by a well-known resonance method.

The tempered glass sheet of the present invention has a compressive stress layer in a surface thereof. The compressive stress value of the compressive stress layer on the outermost surface is preferably 165 MPa or more, 200 MPa or more, 220 MPa or more, 250 MPa or more, 280 MPa or more, 300 MPa or more, or 310 MPa or more, particularly preferably 320 MPa or more. When the compressive stress value of the compressive stress layer on the outermost surface becomes higher, the Vickers hardness is increased more. Meanwhile, when an excessively large compressive stress is formed in the surface, an internal tensile stress of the tempered glass is increased excessively, and there is a risk in that a dimensional change before and after ion exchange treatment may be increased. Accordingly, the compressive stress value of the compressive stress layer on the outermost surface is preferably 1,000 MPa or less, 900 MPa or less, 700 MPa or less, 680 MPa or less, or 650 MPa or less, particularly preferably 600 MPa or less. There is a tendency that the compressive stress value of the compressive stress layer on the outermost surface is increased when an ion exchange time period is shortened, or the temperature of an ion exchange solution is reduced.

The depth of layer is preferably 50 μm or more, 60 μm or more, 80 μm or more, or 100 μm or more, particularly preferably 120 μm or more. As the depth of layer becomes larger, protrusions or sand grains on a road surface are less liable to reach a tensile stress layer at the time of dropping of a smartphone, and thus the breakage probability of the cover glass can be reduced more. Meanwhile, when the depth of layer is too large, there is a risk in that a dimensional change before and after the ion exchange treatment may be increased. Further, there is a tendency that the compressive stress value of the compressive stress layer on the outermost surface is reduced. Accordingly, the depth of layer is preferably 200 μm or less, 180 μm or less, or 150 μm or less, particularly preferably 140 μm or less. There is a tendency that the depth of layer is increased when the ion exchange time period is prolonged, or the temperature of the ion exchange solution is increased.

The tempered glass sheet of the present invention has a thickness of preferably 2.0 mm or less, 1.5 mm or less, 1.3 mm or less, 1.1 mm or less, 1.0 mm or less, or 0.9 mm or less, particularly preferably 0.8 mm or less. As the thickness becomes smaller, the mass of the tempered glass sheet can be reduced more. Meanwhile, when the thickness is too small, it becomes difficult to obtain desired mechanical strength. Accordingly, the thickness is preferably 0.3 mm or more, 0.4 mm or more, 0.5 mm or more, or 0.6 mm or more, particularly preferably 0.7 mm or more.

A method of manufacturing a tempered glass sheet of the present invention comprises: a preparation step of preparing a glass sheet to be tempered including as a glass composition, in terms of mol %, 50% to 80% of SiO₂, 8% to 25% of Al₂O₃, 0% to 10% of B₂O₃, 3% to 15% of Li₂O, 3% to 21% of Na₂O, 0% to 10% of K₂O, 0% to 10% of MgO, 0% to 10% of ZnO, and 0% to 15% of P₂O₅; and an ion exchange step of subjecting the glass sheet to be tempered to ion exchange treatment a plurality of times, to thereby obtain a tempered glass sheet having a compressive stress layer in a surface thereof. The method of manufacturing a tempered glass sheet of the present invention has a feature of performing the ion exchange treatment a plurality of times, but the tempered glass sheet of the present invention encompasses not only the case of performing the ion exchange treatment a plurality of times, but also the case of performing the ion exchange treatment only once.

A method of manufacturing the glass to be tempered is, for example, as described below. As a preferred method, first, glass raw materials blended so as to give a desired glass composition are loaded into a continuous melting furnace, heated to be melted at 1,400° C. to 1,700° C., and fined. After that, the molten glass is supplied to a forming apparatus and formed into a sheet shape, followed by cooling. As a method of cut processing, into predetermined dimensions, the glass having been formed into a sheet shape, a well-known method may be adopted.

As a method of forming the molten glass into a sheet shape, an overflow down-draw method is preferred. In the overflow down-draw method, a surface to serve as the surface of the glass sheet is not brought into contact with the surface of the forming body refractory, and is formed into a sheet shape in a state of a free surface. Thus, a glass sheet having satisfactory surface quality can be manufactured inexpensively without polishing. Further, in the overflow down-draw method, alumina-based refractory or zirconia-based refractory is used as the forming body refractory. Moreover, the tempered glass sheet of the present invention (glass sheet to be tempered) has good compatibility with the alumina-based refractory or the zirconia-based refractory (particularly the alumina-based refractory), and hence has a property of hardly generating bubbles, stones, or the like through a reaction with the refractory.

Various forming methods other than the overflow down-draw method may also be adopted. For example, forming methods such as a float method, a down-draw method (such as a slot down-draw method or a re-draw method), a roll out method, and a press method may be adopted.

At the time of forming of the molten glass, the molten glass is preferably cooled in a temperature region of from the annealing point of the molten glass to the strain point of the molten glass at a cooling rate of 3° C./min or more and less than 1,000° C./min. The lower limit of the range of the cooling rate is preferably 10° C./min or more, 20° C./min or more, or 30° C./min or more, particularly preferably 50° C./min or more, and the upper limit thereof is preferably less than 1,000° C./min, or less than 500° C./min, particularly preferably less than 300° C./min. When the cooling rate is too high, the structure of the glass becomes rough, and it becomes difficult to increase the Vickers hardness after the ion exchange treatment. Meanwhile, when the cooling rate is too low, the manufacturing efficiency of the glass sheet is reduced.

In the method of manufacturing a tempered glass sheet of the present invention, the ion exchange treatment is performed a plurality of times. As the ion exchange treatment performed a plurality of times, it is preferred to perform ion exchange treatment in which the glass sheet to be tempered is immersed in a molten salt containing a KNO₃ molten salt, and then perform ion exchange treatment in which the glass sheet to be tempered is immersed in a molten salt containing a NaNO₃ molten salt. With this configuration, while a large depth of layer is ensured, the compressive stress value of the compressive stress layer on the outermost surface can be increased.

In particular, in the method of manufacturing a tempered glass sheet of the present invention, it is preferred to perform ion exchange treatment (first ion exchange step) in which the glass sheet to be tempered is immersed in a NaNO₃ molten salt or a mixed molten salt of NaNO₃ and KNO₃, and then perform ion exchange treatment (second ion exchange step) in which the glass sheet to be tempered is immersed in a mixed molten salt of KNO₃ and LiNO₃. With this configuration, a non-monotonic stress profile illustrated in each of FIG. 1 and FIG. 2 , that is, a stress profile having at least a first peak, a second peak, a first bottom, and a second bottom can be formed. As a result, the breakage probability of the cover glass can be significantly reduced at the time of dropping of a smartphone.

In the first ion exchange step, a Li ion in the glass and a Na ion in the molten salt are ion exchanged with each other, and in the case of using the mixed molten salt of NaNO₃ and KNO₃, a Na ion in the glass and a K ion in the molten salt are further ion exchanged with each other. Herein, the ion exchange between a Li ion in the glass and a Na ion in the molten salt is faster and more efficient than the ion exchange between a Na ion in the glass and a K ion in the molten salt. In the second ion exchange step, a Na ion in the vicinity of the glass surface (a shallow region from the outermost surface to a sheet thickness of 20%) and a Li ion in the molten salt are ion exchanged with each other, and besides, a Na ion in the vicinity of the glass surface (the shallow region from the outermost surface to a sheet thickness of 20%) and a K ion in the molten salt are ion exchanged with each other. That is, in the second ion exchange step, while a Na ion in the vicinity of the glass surface is released, a K ion, which has a large ionic radius, can be introduced. As a result, while a large depth of layer is maintained, the compressive stress value of the compressive stress layer on the outermost surface can be increased.

In the first ion exchange step, the temperature of the molten salt is preferably from 360° C. to 400° C., and the ion exchange time period is preferably from 30 minutes to 6 hours. In the second ion exchange step, the temperature of the ion exchange solution is preferably from 370° C. to 400° C., and the ion exchange time period is preferably from 15 minutes to 3 hours.

In order to form the non-monotonic stress profile, it is preferred that the concentration of NaNO₃ be higher than the concentration of KNO₃ in the mixed molten salt of NaNO₃ and KNO₃ to be used in the first ion exchange step, and that the concentration of KNO₃ be higher than the concentration of LiNO₃ in the mixed molten salt of KNO₃ and LiNO₃ to be used in the second ion exchange step.

In the mixed molten salt of NaNO₃ and KNO₃ to be used in the first ion exchange step, the concentration of KNO₃ is preferably 0 mass % or more, 0.5 mass % or more, 1 mass % or more, 5 mass % or more, 7 mass % or more, 10 mass % or more, or 15 mass % or more, particularly preferably from 20 mass % to 90 mass %. When the concentration of KNO₃ is too high, there is a risk in that the compressive stress value obtained through ion exchange between a Li ion in the glass and a Na ion in the molten salt may be excessively reduced. In addition, when the concentration of KNO₃ is too low, there is a risk in that measurement of a stress with a surface stress meter FSM-6000 may become difficult.

In the mixed molten salt of KNO₃ and LiNO₃ to be used in the second ion exchange step, the concentration of LiNO₃ is preferably from more than 0 mass % to 5 mass %, from more than 0 mass % to 3 mass %, or from more than 0 mass % to 2 mass %, particularly preferably from 0.1 mass % to 1 mass %. When the concentration of LiNO₃ is too low, it becomes difficult to release a Na ion in the vicinity of the glass surface. Meanwhile, when the concentration of LiNO₃ is too high, there is a risk in that the compressive stress value obtained through ion exchange between a Na ion in the vicinity of the glass surface and a K ion in the molten salt may be excessively reduced.

Example 1

The present invention is hereinafter described with reference to Examples. The following Examples are merely illustrative. The present invention is by no means limited to the following Examples.

The glass compositions and glass characteristics of Examples (Sample Nos. 1 to 35 and 38 to 215) of the present invention and Comparative Examples (Sample Nos. 36 and 37) are shown in Tables 1 to 22. In the tables, the “N.A.” means “unmeasured”, the “(Na−Li)/(Al+B+P)” means the molar ratio ([Na₂O]−[Li₂O])/([Al₂O₃]+[B₂O₃]+[P₂O₅]), the “(B+Na−P)/(Al+Li)” means the molar ratio ([B₂O₃]+[Na₂O]−[P₂O₅])/([Al₂O₃]+[Li₂O]), and the “Si+1.2P−3Al−2Li−1.5Na−K−B” means the [SiO₂]+1.2×[P₂O₅]−3×[Al₂O₃]−2×[Li₂O]−1.5×[Na₂O]−[K₂O]−[B₂O₃].

TABLE 1 (mol %) No. 1 No. 2 No. 3 No. 4 No. 5 No. 6 No. 7 No. 8 No. 9 No. 10 SiO₂ 59.07 59.07 60.07 60.07 61.07 61.07 61.07 61.07 61.07 61.07  Al₂O₃ 17.81 15.81 17.81 15.81 18.81 17.81 16.81 16.81 15.81 15.81  B₂O₃ 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 Li₂O 8.34 8.34 8.34 8.34 7.34 7.34 8.34 7.34 7.34 8.34 Na₂O 11.10 13.10 10.10 12.10 9.10 10.10 10.10 11.10 12.10 11.10  K₂O 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 MgO 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 ZnO 1.16 1.16 1.16 1.16 1.16 1.16 1.16 1.16 1.16 1.16 P₂O₅ 2.47 2.47 2.47 2.47 2.47 2.47 2.47 2.47 2.47 2.47 SnO₂ 0.04 0.04 0.04 0.04 0.04 0.04 0.04 0.04 0.04 0.04 (Na − Li)/(Al + B + P) 0.136 0.260 0.087 0.205 0.083 0.136 0.091 0.195 0.260  0.151 (B + Na − P)/(Al + Li) 0.330 0.440 0.292 0.399 0.253 0.303 0.303 0.357 0.416  0.357 Si + 1.2P − 3Al − 2Li − −24.72 −21.72 −22.22 −19.22 −20.72 −19.22 −18.22 −17.72 −16.22 −16.72  1.5Na − K − B ρ (g/cm³) 2.452 2.459 2.445 2.451 2.438 2.440 2.441 2.444 2.447  2.443 α_(30-380° C.) (×10⁻⁷/° C.) 87 95 84 91 75 83 81 85 89 88    Ts (° C.) 856 N.A. N.A. N.A. 915 889 874 867 861 844    10^(2.5) dPa · s (° C.) 1,518 1,475 1,535 1,504 1,561 1,560 1,547 1,552 1,535 1,524    TL ( ° C.) 1,049 916 1,088 973 1,125 1,078 1,085 1,035 976 1,056>    logη at TL (dPa · s) 5.3 6.4 3.9 5.9 5.2 5.4 5.2 5.6 6.1 5.2< E (GPa) N.A. N.A. N.A. N.A. N.A. N.A. N.A. N.A. N.A. N.A. CS_(K) (MPa) 1,248 1,129 1,292 1,142 1,389 1,309 1,248 1,264 1,198 1,152    DOL_ZERO_(K) (μm) 20 24 19 24 16 19 19 21 24 22    CS_(Na) (MPa) 287 201 312 208 279 269 269 248 211 236    DOL_ZERO_(Na) (μm) 125 121 126 123 134 123 123 128 126 143   

TABLE 2 (mol %) No. 11 No. 12 No. 13 No. 14 No. 15 No. 16 No. 17 No. 18 No. 19 No. 20 SiO₂ 61.07 63.07 61.07 63.07 63.07 61.07 61.07 61.07 59.07 59.07 Al₂O₃ 17.81 15.81 17.81 15.81 17.81 15.81 15.81 17.81 17.81 15.81 B₂O₃ 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 2.00 2.00 Li₂O 8.34 8.34 8.34 7.34 8.34 7.34 8.34 8.34 8.34 8.34 Na₂O 9.10 11.10 11.10 12.10 9.10 12.10 11.10 9.10 11.10 13.10 K₂O 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 MgO 0.00 0.00 0.00 0.00 0.00 2.00 2.00 2.00 0.00 0.00 ZnO 1.16 1.16 1.16 1.16 1.16 1.16 1.16 1.16 1.16 1.16 P₂O₅ 2.47 0.47 0.47 0.47 0.47 0.47 0.47 0.47 0.47 0.47 SnO₂ 0.04 0.04 0.04 0.04 0.04 0.04 0.04 0.04 0.04 0.04 (Na − Li)/(Al + B + P) 0.037 0.169 0.151 0.292 0.041 0.292 0.169 0.041 0.136 0.260 (B + Na − P)/(Al + Li) 0.253 0.440 0.406 0.502 0.330 0.502 0.440 0.330 0.483 0.606 Si + 1.2P − 3Al − 2Li − −19.72 −17.12 −25.12 −16.62 −20.12 −18.62 −19.12 −22.12 −29.12 −26.12 1.5Na − K − B ρ (g/cm³) 2.437 2.454 2.460 2.457 2.446 2.471 2.469 2.463 2.450 2.462 α_(30-380° C.) (×10⁻⁷/° C.) 78 87 87 89 79 89 88 78 86 92 Ts (° C.) N.A. N.A. N.A. 823 N.A. 806 N.A. N.A. 816 743 10^(2.5) dPa · s (° C.) 1,550 1,527 1,528 1,535 1,558 1,489 1,480 1,507 1,487 1,449 TL ( ° C.) 1,125 1,032 1,070 984 1,134 957 1,018 1,230 1,055 904 logη at TL (dPa · s) 4.9 5.1 5.1 5.7 4.9 5.7 5 3.9 5 5.6 E (GPa) N.A. 80 80 N.A. N.A. N.A. N.A. N.A. 78 78 CS_(K) (MPa) 1,326 967 1,165 1,083 1,449 1,170 1,149 1,460 1,228 932 DOL_ZERO_(K) (μm) 18 18 17 17 16 14 12 10 14 14 CS_(Na) (MPa) 299 278 305 236 304 224 262 309 321 298 DOL_ZERO_(Na) (μm) 136 116 119 119 137 98 104 104 104 93

TABLE 3 (mol %) No. 21 No. 22 No. 23 No. 24 No. 25 No. 26 No. 27 No. 28 No. 29 No. 30 SiO₂ 60.07 60.07 61.07 61.07 61.07 61.07 59.07 59.07 59.07 59.07 Al₂O₃ 17.81 15.81 18.81 17.81 16.81 16.81 17.81 16.81 18.81 18.81 B₂O₃ 2.00 2.00 2.00 2.00 2.00 2.00 2.00 2.00 2.00 2.00 Li₂O 8.34 8.34 7.34 7.34 8.34 7.34 7.34 8.34 8.34 7.34 Na₂O 10.10 12.10 9.10 10.10 10.10 11.10 12.10 12.10 10.10 11.10 K₂O 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 MgO 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 ZnO 1.16 1.16 1.16 1.16 1.16 1.16 1.16 1.16 1.16 1.16 P₂O₅ 0.47 0.47 0.47 0.47 0.47 0.47 0.47 0.47 0.47 0.47 SnO₂ 0.04 0.04 0.04 0.04 0.04 0.04 0.04 0.04 0.04 0.04 (Na − Li)/(Al + B + P) 0.087 0.205 0.083 0.136 0.091 0.195 0.235 0.195 0.083 0.177 (B + Na − P)/(Al + Li) 0.445 0.564 0.406 0.462 0.462 0.523 0.542 0.542 0.428 0.483 Si + 1.2P − 3Al − 2Li − −26.62 −23.62 −25.12 −23.62 −22.62 −22.12 −28.62 −27.62 −30.62 −30.12 1.5Na − K − B ρ (g/cm³) 2.442 2.455 2.438 2.438 2.440 2.443 2.452 2.456 2.450 2.450 α_(30-380° C.) (×10⁻⁷/° C.) 82 89 74 80 83 84 88 90 82 83 Ts (° C.) N.A. 756 882 862 827 821 819 777 850 856 10^(2.5) dPa · s (° C.) 1,496 1,488 1,530 1,530 1,508 1,524 1,509 1,474 1,493 1,507 TL ( ° C.) 1,089 967 1,060 1,078 1,091 1,030 991 985 1,051 1,040 logη at TL (dPa · s) 4.9 5.3 5.5 5.2 4.8 5.3 5.6 5.3 5.2 5.4 E (GPa) N.A. N.A. N.A. N.A. N.A. N.A. 76 78 N.A. N.A. CS_(K) (MPa) 1,293 860 1,438 1,385 1,218 1,230 1,264 1,087 1,439 1,433 DOL_ZERO_(K) (μm) 14 13 12 15 13 15 14 14 12 14 CS_(Na) (MPa) 302 259 297 312 324 271 282 292 309 280 DOL_ZERO_(Na) (μm) 107 100 111 119 108 111 106 92 112 118

TABLE 4 (mol %) No. 31 No. 32 No. 33 No. 34 No. 35 No. 36 No. 37 SiO₂ 59.07 61.07  61.07 61.07 63.58 61.07  61.07  Al₂O₃ 17.81 15.81  15.81 17.81 16.55 17.81  19.81  B₂O₃ 2.00 2.00 2.00 2.00 0.00 2.00 0.00 Li₂O 9.34 7.34 8.34 8.34 8.19 4.34 8.34 Na₂O 10.10 12.10  11.10 9.10 8.09 13.10  7.10 K₂O 0.00 0.00 0.00 0.00 0.52 0.00 0.00 MgO 0.00 0.00 0.00 0.00 0.33 0.00 0.00 ZnO 1.16 1.16 1.16 1.16 0.00 1.16 1.16 P₂O₅ 0.47 0.47 0.47 0.47 2.70 0.47 2.47 SnO₂ 0.04 0.04 0.04 0.04 0.04 0.04 0.04 (Na − Li)/(Al + B + P) 0.037  0.260 0.151 0.037 −0.056  0.432 −0.056 (B + Na − P)/(Al + Li) 0.428  0.589 0.523 0.406 0.164  0.660  0.164 Si + 1.2P − 3Al − 2Li − −29.62 −20.62  −21.12 −24.12 −11.87 −22.12  −22.72  1.5Na − K − B ρ (g/cm³) 2.450  2.449 2.448 2.435 2.404  2.442  2.437 α_(30-380° C.) (×10⁻⁷/° C.) 84 87    86 78 79 83    68    Ts (° C.) N.A. 785    781 N.A. N.A. 891    917    10^(2.5) dPa · s (° C.) 1,480 1,508    1,487 1,519 1,593 1,564    1,541    TL ( ° C.) 1,068 938>   1,034 1,117 1,145 938>   1,343<    logη at TL (dPa · s) 4.8 5.8< 4.9 4.9 5.14 7.0< 3.5> E (GPa) N.A. N.A. N.A. N.A. 77 N.A. N.A. CS_(K) (MPa) 1,225 1,045    1,026 1,379 1,021 1,474    1,376    DOL_ZERO_(K) (μm) 12 15    13 14 26 21    11    CS_(Na) (MPa) 340 255    280 330 310 163    324    DOL_ZERO_(Na) (μm) 112 105    105 115 131 132    116   

TABLE 5 (mol %) No. 38 No. 39 No. 40 No. 41 No. 42 No. 43 SiO₂ 62.24 62.24 60.24 60.24 62.24 62.24 Al₂O₃ 17.81 15.81 17.81 15.81 17.81 15.81 B₂O₃ 2.00 2.00 2.00 2.00 0.00 0.00 Li₂O 8.34 8.34 8.34 8.34 8.34 8.34 Na₂O 9.10 11.10 11.10 13.10 9.10 11.10 K₂O 0.00 0.00 0.00 0.00 0.00 0.00 MgO 0.00 0.00 0.00 0.00 0.00 0.00 ZnO 0.00 0.00 0.00 0.00 0.00 0.00 P₂O₅ 0.47 0.47 0.47 0.47 2.47 2.47 SnO₂ 0.04 0.04 0.04 0.04 0.04 0.04 Fe₂O₃ 0.01 0.01 0.01 0.01 0.01 0.01 TiO₂ 0.01 0.01 0.01 0.01 0.01 0.01 Cl 0.01 0.01 0.01 0.01 0.01 0.01 (Na − Li)/(Al + B + P) 0.04 0.15 0.14 0.26 0.04 0.15 (B + Na − P)/(Al + Li) 0.41 0.52 0.48 0.61 0.25 0.36 Si + 1.2P − 3Al − 2Li − −22.96 −19.96 −27.96 −24.96 −18.56 −15.56 1.5Na − K − B ρ (g/cm³) 2.4099 2.4257 2.4265 2.4415 2.4127 2.4219 α_(30-380° C.) (×10⁻⁷/° C.) 80.3 86.9 86.9 91.8 80.8 88.6 Ts (° C.) 877 775 827 738 917 N.A. 10^(2.5) dPa · s (° C.) 1,538 1,517 1,516 1,467 1,580 1,548 TL ( ° C.) 1,152 1,047 1,030 914 1,126 1,029 logη at TL (dPa · s) 4.66 4.87 5.33 5.55 5.19 5.62 Acid resistance (HCl 5 34.8< N.A. 34.8< N.A. 34.8 28.5 wt % 80° C. 24 h) Alkali resistance (NaOH 0.8 N.A. 0.8 N.A. 0.9 0.8 5 wt % 80° C. 6 h) E (GPa) 77.6 78.3 78.0 78.5 77.9 76.9 CS_(K) (MPa) 1,307 932 1,124 751 1,262 1,016 DOL_ZERO_(K) (μm) 15.7 14.8 15.4 13.1 21.4 24.4 CS_(Na) (MPa) 279 221 272 212 258 197 DOL_ZERO_(Na) (μm) 135.7 118.8 116.2 105.0 153.7 158.0 (mol %) No. 44 No. 45 No. 46 No. 47 No. 48 SiO₂ 60.24 60.24 58.24 56.24 58.24 Al₂O₃ 17.81 15.81 17.81 17.81 17.81 B₂O₃ 0.00 0.00 2.00 2.00 0.00 Li₂O 8.34 8.34 8.34 8.34 8.34 Na₂O 11.10 13.10 9.10 11.10 9.10 K₂O 0.00 0.00 4.00 4.00 4.00 MgO 0.00 0.00 0.00 0.00 0.00 ZnO 0.00 0.00 0.00 0.00 0.00 P₂O₅ 2.47 2.47 0.47 0.47 2.47 SnO₂ 0.04 0.04 0.04 0.04 0.04 Fe₂O₃ 0.01 0.01 0.01 0.01 0.01 TiO₂ 0.01 0.01 0.01 0.01 0.01 Cl 0.01 0.01 0.01 0.01 0.01 (Na − Li)/(Al + B + P) 0.14 0.26 0.04 0.14 0.04 (B + Na − P)/(Al + Li) 0.33 0.44 0.41 0.48 0.25 Si + 1.2P − 3Al − 2Li − −23.56 −20.56 −30.96 −35.96 −26.56 1.5Na − K − B ρ (g/cm³) 2.4277 2.436 2.4418 2.4581 2.4416 α_(30-380° C.) (×10⁻⁷/° C.) 88.7 94.8 96.9 103.9 99.8 Ts (° C.) 877 N.A. 773 N.A. N.A. 10^(2.5) dPa · s (° C.) 1,546 1,498 1,492 1,461 1,537 TL ( ° C.) 1,125 1,066 1,216 941 1,120 logη at TL (dPa · s) 4.87 4.90 3.74 5.25 4.78< Acid resistance (HCl 5 34.8< 34.8< N.A. N.A. 34.8< wt % 80° C. 24 h) Alkali resistance (NaOH 0.9 0.7 N.A. N.A. 0.9 5 wt % 80° C. 6 h) E (GPa) 77.3 76.9 77.8 78.8 77.1 CS_(K) (MPa) 1,151 1,018 810 889 1,307 DOL_ZERO_(K) (μm) 23.6 26.8 23.1 N.A. 36.1 CS_(Na) (MPa) 324 165 202 N.A. 259 DOL_ZERO_(Na) (μm) 131.9 133.5 85.6 N.A. 95.1

TABLE 6 (mol %) No. 49 No. 50 No. 51 No. 52 No. 53 SiO₂ 56.24 61.24 61.24 60.24 62.24 Al₂O₃ 17.81 16.81 15.81 16.81 15.81 B₂O₃ 0.00 0.00 0.00 0.00 0.50 Li₂O 8.34 8.34 8.34 8.34 8.34 Na₂O 11.10 11.10 12.10 12.10 11.10 K₂O 4.00 0.00 0.00 0.00 0.00 MgO 0.00 0.00 0.00 0.00 0.00 ZnO 0.00 0.00 0.00 0.00 0.00 P₂O₅ 2.47 2.47 2.47 2.47 1.97 SnO₂ 0.04 0.04 0.04 0.04 0.04 Fe₂O₃ 0.01 0.01 0.01 0.01 0.01 TiO₂ 0.01 0.01 0.01 0.01 0.01 Cl 0.01 0.01 0.01 0.01 0.01 (Na − Li)/(Al + B + P) 0.14 0.14 0.21 0.19 0.15 (B + Na − P)/(Al + Li) 0.33 0.34 0.40 0.38 0.40 Si + 1.2P − 3Al − 2Li − −31.56 −19.56 −18.06 −22.06 −16.66 1.5Na − K − B ρ (g/cm³) 2.4554 2.4234 2.4272 2.4309 2.4189 α_(30-380° C.) (×10⁻⁷/° C.) 107.4 88.4 92.1 92.1 87.6 Ts (° C.) N.A. 860 N.A. N.A. N.A. 10^(2.5) dPa · s (° C.) 1,494 1,547 1,528 1,529 1,537 TL ( ° C.) 1,018 N.A. N.A. N.A. N.A. logη at TL (dPa · s) 5.39 N.A. N.A. N.A. N.A. Acid resistance (HCl 5 34.8< N.A. N.A. N.A. N.A. wt % 80° C. 24 h) Alkali resistance (NaOH 0.9 N.A. N.A. N.A. N.A. 5 wt % 80° C. 6 h) E (GPa) 77.4 76.8 76.6 76.6 76.6 CS_(K) (MPa) N.A. 915 894 1,173 806 DOL_ZERO_(K) (μm) N.A. 28.8 29.9 31.2 24.9 CS_(Na) (MPa) N.A. 255 194 227 237 DOL_ZERO_(Na) (μm) N.A. 132.3 140.8 150.6 147.3 (mol %) No. 54 No. 55 No. 56 No. 57 No. 58 SiO₂ 62.24 60.24 60.24 62.24 63.07 Al₂O₃ 15.81 17.81 15.81 15.81 16.81 B₂O₃ 0.00 0.00 0.00 0.50 0.00 Li₂O 5.84 5.84 5.84 5.84 4.34 Na₂O 11.10 11.10 13.10 11.10 14.10 K₂O 2.50 2.50 2.50 2.50 0.00 MgO 0.00 0.00 0.00 0.00 0.00 ZnO 0.00 0.00 0.00 0.00 1.16 P₂O₅ 2.47 2.47 2.47 1.97 0.47 SnO₂ 0.04 0.04 0.04 0.04 0.04 Fe₂O₃ 0.01 0.01 0.01 0.01 0.01 TiO₂ 0.01 0.01 0.01 0.01 0.00 Cl 0.01 0.01 0.01 0.01 0.01 (Na − Li)/(Al + B + P) 0.29 0.26 0.40 0.29 0.56 (B + Na − P)/(Al + Li) 0.40 0.36 0.49 0.44 0.64 Si + 1.2P − 3Al − 2Li − −13.06 −21.06 −18.06 −14.16 −16.62 1.5Na − K − B ρ (g/cm³) 2.4262 2.4323 2.4401 2.4249 2.4604 α_(30-380° C.) (×10⁻⁷/° C.) 96.7 95.2 102.5 95.3 90.5 Ts (° C.) N.A. 893 N.A. N.A. 890 10^(2.5) dPa · s (° C.) 1,589 1,593 1,544 1,576 1,592 TL ( ° C.) N.A. N.A. N.A. N.A. N.A. logη at TL (dPa · s) N.A. N.A. N.A. N.A. N.A. Acid resistance (HCl 5 N.A. N.A. N.A. N.A. 33.3< wt % 80° C. 24 h) Alkali resistance (NaOH N.A. N.A. N.A. N.A. 0.6 5 wt % 80° C. 6 h) E (GPa) 74.1 75.2 74.6 74.5 76.8 CS_(K) (MPa) 903 986 922 907 1,166 DOL_ZERO_(K) (μm) 50.0 46.7 51.4 39.5 28.6 CS_(Na) (MPa) 121 162 99 148 153 DOL_ZERO_(Na) (μm) 129.5 131.3 92.7 103.9 124.0

TABLE 7 (mol %) No. 59 No. 60 No. 61 No. 62 No. 63 No. 64 SiO₂ 63.07 66.40 66.40 63.07 63.07 63.07 Al₂O₃ 16.81 8.51 8.51 16.81 16.81 16.81 B₂O₃ 0.00 0.00 0.00 0.00 0.00 0.00 Li₂O 4.34 4.21 4.21 4.34 4.34 4.34 Na₂O 13.10 8.55 8.55 13.10 13.10 13.10 K₂O 1.00 3.73 3.73 0.00 0.00 0.00 MgO 0.00 0.00 0.00 1.00 0.00 0.00 ZnO 1.16 6.02 4.02 1.16 1.16 1.16 P₂O₅ 0.47 0.81 2.81 0.47 1.47 0.47 SnO₂ 0.04 0.04 0.04 0.04 0.04 0.04 Fe₂O₃ 0.01 0.01 0.01 0.01 0.01 0.01 TiO₂ 0.00 1.74 1.74 0.00 0.00 1.00 Cl 0.01 0.01 0.01 0.01 0.01 0.01 (Na − Li)/(Al + B + P) 0.51 0.47 0.38 0.51 0.48 0.51 (B + Na − P)/(Al + Li) 0.60 0.61 0.45 0.60 0.55 0.60 Si + 1.2P − 3Al − 2Li − −16.12 16.89 19.29 −15.12 −13.92 −15.12 1.5Na − K − B ρ (g/cm³) 2.4613 2.5352 2.4784 2.46 2.4464 2.4583 α_(30-380° C.) (×10⁻⁷/° C.) 93.3 90.6 90.4 86.1 85.8 86 Ts (° C.) 902 918 N.A. 903 918 903 10^(2.5) dPa · s (° C.) 1,488 1,603 1,531 1,591 1,613 1,597 TL ( ° C.) N.A. N.A. N.A. N.A. N.A. N.A. logη at TL (dPa · s) N.A. N.A. N.A. N.A. N.A. N.A. Acid resistance (HCl 5 33.3< 0 N.A. 33.3< 33.3 N.A. wt % 80° C. 24 h) Alkali resistance (NaOH 0.6 0.6 N.A. 0.1 0.7 N.A. 5 wt % 80° C. 6 h) E (GPa) 76.9 75.1 72.6 77.5 75.4 76.4 CS_(K) (MPa) 1,138 757 660 1,262 1,202 1,265 DOL_ZERO_(K) (μm) 32.9 33.8 46.0 21.8 28.2 24.6 CS_(Na) (MPa) 151 74 35 116 127 167 DOL_ZERO_(Na) (μm) 143.6 57.1 64.8 127.9 143.6 122.8 (mol %) No. 65 No. 66 No. 67 No. 68 SiO₂ 63.07 63.07 63.07 63.07 Al₂O₃ 16.81 17.21 15.71 15.71 B₂O₃ 0.00 0.60 0.60 0.60 Li₂O 4.34 4.34 4.34 4.34 Na₂O 13.10 13.10 13.10 13.10 K₂O 0.00 0.00 0.00 1.50 MgO 0.00 0.00 0.00 0.00 ZnO 2.16 1.16 1.16 1.16 P₂O₅ 0.47 0.47 1.97 0.47 SnO₂ 0.04 0.04 0.04 0.04 Fe₂O₃ 0.01 0.01 0.01 0.01 TiO₂ 0.00 0.00 0.00 0.00 Cl 0.01 0.01 0.01 0.01 (Na − Li)/(Al + B + P) 0.51 0.48 0.48 0.52 (B + Na − P)/(Al + Li) 0.60 0.61 0.58 0.66 Si + 1.2P − 3Al − 2Li − −15.12 −16.92 −10.62 −13.92 1.5Na − K − B ρ (g/cm³) 2.4715 2.4483 2.4369 2.4577 α_(30-380° C.) (×10⁻⁷/° C.) 85.2 85.9 85.8 94.4 Ts (° C.) 899 904 873 828 10^(2.5) dPa · s (° C.) 1,596 1,598 1,599 1,582 TL ( ° C.) N.A. N.A. N.A. N.A. logη at TL (dPa · s) N.A. N.A. N.A. N.A. Acid resistance (HCl 5 N.A. N.A. N.A. N.A. wt % 80° C. 24 h) Alkali resistance (NaOH N.A. N.A. N.A. N.A. 5 wt % 80° C. 6 h) E (GPa) 77.1 76.0 73.8 76.0 CS_(K) (MPa) 1,290 1,264 1,033 964 DOL_ZERO_(K) (μm) 22.2 25.4 27.8 26.1 CS_(Na) (MPa) 170 175 147 153 DOL_ZERO_(Na) (μm) 127.7 133.1 141.1 88.2

TABLE 8 (mol %) No. 69 No. 70 No. 71 No. 72 No. 73 SiO₂ 63.07 63.07 63.22 63.94 66.40 Al₂O₃ 14.21 17.81 17.00 12.71 10.25 B₂O₃ 0.60 0.00 0.40 0.40 0.00 Li₂O 4.34 4.34 4.34 8.34 4.21 Na₂O 13.10 13.10 13.10 11.10 8.55 K₂O 1.50 0.00 1.50 0.50 4.23 MgO 0.00 0.00 0.00 0.50 0.00 ZnO 1.16 1.16 0.00 0.00 5.52 P₂O₅ 1.97 0.47 0.40 2.47 0.81 SnO₂ 0.04 0.04 0.04 0.04 0.04 Fe₂O₃ 0.01 0.01 0.01 0.01 0.01 TiO₂ 0.00 0.00 0.00 0.00 0.00 Cl 0.01 0.01 0.01 0.01 0.01 (Na − Li)/(Al + B + P) 0.52 0.48 0.49 0.18 0.39 (B + Na − P)/(Al + Li) 0.63 0.57 0.61 0.43 0.53 Si + 1.2P − 3Al − 2Li − −7.62 −18.12 −17.53 −5.46 11.17 1.5Na − K − B ρ (g/cm³) 2.4417 2.454 2.438 2.4142 2.5106 α_(30-380° C.) (×10⁻⁷/° C.) 93.8 84.8 93.3 88.7 92.8 Ts (° C.) N.A. 937 865 N.A. N.A. 10^(2.5) dPa · s (° C.) 1,567 1,613 1,611 1,486 1,527 TL ( ° C.) N.A. N.A. 943 N.A. N.A. logη at TL (dPa · s) N.A. N.A. 6.69 N.A. N.A. Acid resistance (HCl 5 2.4 N.A. 33.3< 0.1 0 wt % 80° C. 24 h) Alkali resistance (NaOH 0.2 N.A. 0.6 0.6 0.6 5 wt % 80° C. 6 h) E (GPa) 73.3 77.0 75.8 75.7 74.1 CS_(K) (MPa) 1,041 N.A. 1,026 930 792 DOL_ZERO_(K) (μm) 40.8 N.A. 32.0 26.6 40.6 CS_(Na) (MPa) 157 N.A. 152 119 82 DOL_ZERO_(Na) (μm) 70.3 N.A. 121.9 118.2 69.2 (mol %) No. 74 No. 75 No. 76 No. 77 No. 78 SiO₂ 64.76 65.76 64.76 65.76 64.24 Al₂O₃ 16.25 16.25 16.25 16.25 17.81 B₂O₃ 0.10 0.10 0.10 0.10 0.00 Li₂O 5.20 5.20 5.70 5.70 6.34 Na₂O 11.00 11.00 10.50 10.50 11.10 K₂O 1.25 1.25 1.25 1.25 0.00 MgO 1.00 0.00 1.00 0.00 0.00 ZnO 0.00 0.00 0.00 0.00 0.00 P₂O₅ 0.40 0.40 0.40 0.40 0.47 SnO₂ 0.04 0.04 0.04 0.04 0.04 Fe₂O₃ 0.01 0.01 0.01 0.01 0.01 TiO₂ 0.00 0.00 0.00 0.00 0.00 Cl 0.01 0.01 0.01 0.01 0.01 (Na − Li)/(Al + B + P) 0.35 0.35 0.29 0.29 0.26 (B + Na − P)/(Al + Li) 0.50 0.50 0.46 0.46 0.44 Si + 1.2P − 3Al − 2Li − −11.76 −10.76 −12.01 −11.01 −17.96 1.5Na − K − B ρ (g/cm³) N.A. N.A. N.A. N.A. 2.4243 α_(30-380° C.) (×10⁻⁷/° C.) 87.8 88.7 87.7 87.9 84.8 Ts (° C.) 883 899 877 893 949 10^(2.5) dPa · s (° C.) 1,609 1,639 1,605 1,634 1,617 TL ( ° C.) 961 965 1,016 1,005 1,087 logη at TL (dPa · s) N.A. N.A. N.A. N.A. N.A. Acid resistance (HCl 5 43.2 48.0 34.1 31.4 31.9 wt % 80° C. 24 h) Alkali resistance (NaOH 0.5 0.6 0.5 0.5 N.A. 5 wt % 80° C. 6 h) E (GPa) 76.8 76.0 77.2 76.2 77.6 CS_(K) (MPa) 1,073 1,020 1,058 1,024 1,315 DOL_ZERO_(K) (μm) 30.5 32.1 26.1 30.3 26.9 CS_(Na) (MPa) 229 213 235 236 281 DOL_ZERO_(Na) (μm) 108.0 117.5 115.9 115.1 134.0

TABLE 9 (mol %) No. 79 No. 80 No. 81 No. 82 No. 83 No. 84 SiO₂ 64.61 64.61  62.99 63.58 63.58 63.58 Al₂O₃ 17.81 18.81  17.81 16.55 16.55 15.55 B₂O₃ 0.10 0.10 0.10 0.00 0.00 0.00 Li₂O 6.34 7.34 8.90 9.19 7.19 8.69 Na₂O 9.85 7.85 8.90 7.09 9.09 8.59 K₂O 1.25 1.25 1.25 0.52 0.52 0.52 MgO 0.00 0.00 0.00 0.33 0.33 0.33 ZnO 0.00 0.00 0.00 0.00 0.00 0.00 P₂O₅ 0.00 0.00 0.00 2.70 2.70 2.70 SnO₂ 0.04 0.04 0.04 0.04 0.04 0.04 Fe₂O₃ 0.01 0.01 0.01 0.01 0.01 0.01 TiO₂ 0.00 0.00 0.00 0.00 0.00 0.00 Cl 0.01 0.01 0.01 0.01 0.01 0.01 (Na − Li)/(Al + B + P) 0.20 0.03 0.00 −0.11 0.10 −0.01 (B + Na − P)/(Al + Li) 0.41 0.30 0.34 0.17 0.27 0.24 Si + 1.2P − 3Al − 2Li − −17.63 −19.63  −22.95 −12.37 −11.37 −10.62 1.5Na − K − B ρ (g/cm³) 2.4246  2.4243 N.A. 2.4019 2.4072 2.4076 α_(30-380° C.) (×10⁻⁷/° C.) 86.6 77.5  88.4 79 82 84 Ts (° C.) 936 954    N.A. N.A. 915 N.A. 10^(2.5) dPa · s (° C.) 1,616 1,602    1,556 1,589 1,610 1,575 TL ( ° C.) 1,080 1,270<    N.A. 1,180 1,092 1,107 logη at TL (dPa · s) 5.91 N.A. N.A. N.A. 5.60 N.A. Acid resistance (HCl 5 34.4 34.9  >100 4.1 4.3 2.2 wt % 80° C. 24 h) Alkali resistance (NaOH 0.6 1.4  0.0 0.8 0.7 0.7 5 wt % 80° C. 6 h) E (GPa) 78.3 79.8  N.A. 77.3 75.8 76.6 CS_(K) (MPa) 1,273 1,319    1,071 1,059 1,074 967 DOL_ZERO_(K) (μm) 31.1 22.6  17.3 23.4 30.1 24.9 CS_(Na) (MPa) 294 352    401 388 280 288 DOL_ZERO_(Na) (μm) 116.0 108.4   87.0 113.8 122.3 120.5 (mol %) No. 85 No. 86 No. 87 No. 88 SiO₂ 62.58 66.26 66.26 66.26 Al₂O₃ 17.55 16.25 16.25 16.25 B₂O₃ 0.00 0.10 0.10 0.10 Li₂O 8.19 5.20 5.70 4.70 Na₂O 8.09 10.50 10.00 11.00 K₂O 0.52 1.25 1.25 1.25 MgO 0.33 0.00 0.00 0.00 ZnO 0.00 0.00 0.00 0.00 P₂O₅ 2.70 0.40 0.40 0.40 SnO₂ 0.04 0.04 0.04 0.04 Fe₂O₃ 0.01 0.01 0.01 0.01 TiO₂ 0.00 0.00 0.00 0.00 Cl 0.01 0.01 0.01 0.01 (Na − Li)/(Al + B + P) 0.00 0.32 0.26 0.38 (B + Na − P)/(Al + Li) 0.21 0.48 0.44 0.51 Si + 1.2P − 3Al − 2Li − −15.87 −9.51 −9.76 −9.26 1.5Na − K − B ρ (g/cm³) 2.4091 2.4161 2.4135 2.4133 α_(30-380° C.) (×10⁻⁷/° C.) 79.7 87.4 86.4 87.9 Ts (° C.) 915 917 913 923 10^(2.5) dPa · s (° C.) N.A. 1,644 1,648 1,658 TL ( ° C.) 1,136 990 1,034 939 logη at TL (dPa · s) N.A. N.A. 6.24 N.A. Acid resistance (HCl 5 16.6 12.0 8.4 16.7 wt % 80° C. 24 h) Alkali resistance (NaOH 0.9 0.6 0.6 0.6 5 wt % 80° C. 6 h) E (GPa) 77.1 75.9 75.9 74.9 CS_(K) (MPa) 1,138 1,045 1,039 1,075 DOL_ZERO_(K) (μm) 25.0 38.8 37.0 39.2 CS_(Na) (MPa) 339 240 260 234 DOL_ZERO_(Na) (μm) 111.5 121.2 129.4 114.9

TABLE 10 (mol %) No. 89 No. 90 No. 91 No. 92 No. 93 SiO₂ 65.76 63.36 64.36 63.36 63.36 Al₂O₃ 16.25 17.81 17.81 17.81 17.81 B₂O₃ 0.10 0.10 0.10 0.10 0.10 Li₂O 4.70 8.34 8.34 8.84 8.34 Na₂O 11.50 9.10 8.10 8.60 8.60 K₂O 1.25 1.25 1.25 1.25 1.75 MgO 0.00 0.00 0.00 0.00 0.00 ZnO 0.00 0.00 0.00 0.00 0.00 P₂O₅ 0.40 0.00 0.00 0.00 0.00 SnO₂ 0.04 0.04 0.04 0.04 0.04 Fe₂O₃ 0.01 0.01 0.01 0.01 0.01 TiO₂ 0.00 0.00 0.00 0.00 0.00 Cl 0.01 0.01 0.01 0.01 0.01 (Na − Li)/(Al + B + P) 0.41 0.04 −0.01 −0.01 0.01 (B + Na − P)/(Al + Li) 0.53 0.35 0.31 0.33 0.33 Si + 1.2P − 3Al − 2Li − −10.51 −21.75 −19.25 −22.00 −21.50 1.5Na − K − B ρ (g/cm³) 2.4178 2.4307 2.4217 2.4292 2.4309 α_(30-380° C.) (×10⁻⁷/° C.) 89.5 86.3 84.12 86.9 87.9 Ts (° C.) 902 N.A. N.A. N.A. N.A. 10^(2.5) dPa · s (° C.) 1,656 1,572 1,595 1,570 1,578 TL ( ° C.) 916 1,092 1,137 1,113 1,084 logη at TL (dPa · s) N.A. N.A. 5.20 N.A. N.A. Acid resistance (HCl 5 78.6< 76.4< 74.7< 78.2< 78.3< wt % 80° C. 24 h) Alkali resistance (NaOH 0.6 0.6 0.6 0.6 0.5 5 wt % 80° C. 6 h) E (GPa) 75.1 79.7 79.5 79.9 79.4 CS_(K) (MPa) 1,021 1,033 1,142 1,020 1,023 DOL_ZERO_(K) (μm) 37.5 25.3 27.3 24.7 27.4 CS_(Na) (MPa) 235 354 401 383 360 DOL_ZERO_(Na) (μm) 113.2 119.5 113.8 100.6 104.9 (mol %) No. 94 No. 95 No. 96 No. 97 No. 98 SiO₂ 63.50 63.50 63.50  63.50  62.89 Al₂O₃ 15.56 17.56 15.56  14.56  17.81 B₂O₃ 0.10 0.10 0.10 0.10 0.10 Li₂O 8.10 6.10 6.10 6.10 8.34 Na₂O 8.00 8.00 10.00  11.00  9.10 K₂O 2.15 2.15 2.15 2.15 1.25 MgO 0.00 0.00 0.00 0.00 0.00 ZnO 0.00 0.00 0.00 0.00 0.00 P₂O₅ 2.55 2.55 2.55 2.55 0.47 SnO₂ 0.04 0.04 0.04 0.04 0.04 Fe₂O₃ 0.01 0.01 0.01 0.01 0.01 TiO₂ 0.00 0.00 0.00 0.00 0.00 Cl 0.01 0.01 0.01 0.01 0.01 (Na − Li)/(Al + B + P) −0.01 0.09 0.21 0.28 0.04 (B + Na − P)/(Al + Li) 0.23 0.23 0.35 0.41 0.33 Si + 1.2P − 3Al − 2Li − −10.57 −12.57 −9.57  −8.07  −21.65 1.5Na − K − B ρ (g/cm³) 2.4088 2.4039  2.414  2.4181 2.4268 α_(30-380° C.) (×10⁻⁷/° C.) 87.9 82.6 91.4  93.7  87.9 Ts (° C.) N.A. 938 860    880   N.A. 10^(2.5) dPa · s (° C.) 1,579 1,630 1,606    1,574    1,569 TL ( ° C.) 1,020 1,036 1,014>   1,014>   1,110 logη at TL (dPa · s) N.A. 6.41 N.A. N.A. N.A. Acid resistance (HCl 5 4.8 16.2 8.0  1.2  67.5 wt % 80° C. 24 h) Alkali resistance (NaOH 0.8 0.9 0.8  0.6  0.5 5 wt % 80° C. 6 h) E (GPa) 75.5 74.9 74.3  74.1  78.7 CS_(K) (MPa) 843 1,046 895   N.A. 1,055 DOL_ZERO_(K) (μm) 40.7 44.4 46.9  N.A. 29.0 CS_(Na) (MPa) 287 282 218   N.A. 354 DOL_ZERO_(Na) (μm) 113.8 113.0 108.3   N.A. 108.5

TABLE 11 (mol %) No. 99 No. 100 No. 101 No. 102 No. 103 No. 104 SiO₂ 62.89 62.89 62.89 62.96 63.36 62.96 Al₂O₃ 18.81 17.81 16.81 18.81 18.81 18.81 B₂O₃ 0.10 0.10 0.10 0.10 0.10 0.10 Li₂O 7.34 7.34 8.34 7.34 7.34 7.34 Na₂O 9.10 10.10 10.10 8.60 8.60 8.60 K₂O 1.25 1.25 1.25 0.75 0.75 0.75 MgO 0.00 0.00 0.00 1.00 1.00 0.00 ZnO 0.00 0.00 0.00 0.00 0.00 0.00 P₂O₅ 0.47 0.47 0.47 0.40 0.00 1.40 SnO₂ 0.04 0.04 0.04 0.04 0.04 0.04 Fe₂O₃ 0.01 0.01 0.01 0.01 0.01 0.01 TiO₂ 0.00 0.00 0.00 0.00 0.00 0.00 Cl 0.01 0.01 0.01 0.01 0.01 0.01 (Na − Li)/(Al + B + P) 0.09 0.15 0.10 0.07 0.07 0.06 (B + Na − P)/(Al + Li) 0.33 0.39 0.39 0.32 0.33 0.28 Si + 1.2P − 3Al − 2Li − −22.65 −21.15 −20.15 −21.42 −21.50 −20.22 1.5Na − K − B ρ (g/cm³) 2.426 2.4299 2.4338 2.4301 2.4328 2.4165 α_(30-380° C.) (×10⁻⁷/° C.) 82.6 91.4 93.7 78.1 79 79 Ts (° C.) 930 887 1 921 927 937 10^(2.5) dPa · s (° C.) 1,584 1,584 1,556 1,571 1,573 1,594 TL ( ° C.) 1,086 1,059 1,032 N.A. N.A. N.A. logη at TL (dPa · s) 5.71 N.A. N.A. N.A. N.A. N.A. Acid resistance (HCl 5 77.1 76.6 61.0 55.7 51.8 38.4 wt % 80° C. 24 h) Alkali resistance (NaOH 0.7 0.5 0.5 0.8 0.7 1.0 5 wt % 80° C. 6 h) E (GPa) 78.8 78.3 79.1 79.7 80.6 78.2 CS_(K) (MPa) 1,176 1,056 894 1,301 1,345 1,227 DOL_ZERO_(K) (μm) 29.4 29.6 25.3 18.7 18.1 21.3 CS_(Na) (MPa) 313 295 330 345 362 324 DOL_ZERO_(Na) (μm) 121.7 124.0 102.4 108.4 97.4 108.6 (mol %) No. 105 No. 106 No. 107 No. 108 SiO₂ 62.96 65.65 64.10 64.10 Al₂O₃ 18.10 17.56 18.10 18.10 B₂O₃ 0.10 0.10 0.10 0.10 Li₂O 8.72 6.10 6.33 6.33 Na₂O 7.93 8.00 8.24 8.24 K₂O 0.75 2.15 1.69 0.04 MgO 0.00 0.00 0.00 0.00 ZnO 0.00 0.00 0.00 0.00 P₂O₅ 1.40 0.40 1.40 3.05 SnO₂ 0.04 0.04 0.04 0.04 Fe₂O₃ 0.01 0.01 0.01 0.01 TiO₂ 0.00 0.00 0.00 0.00 Cl 0.01 0.01 0.01 0.01 (Na − Li)/(Al + B + P) −0.04 0.11 0.10 0.09 (B + Na − P)/(Al + Li) 0.25 0.33 0.28 0.22 Si + 1.2P − 3Al − 2Li − −19.84 −13.00 −15.33 −11.70 1.5Na − K − B ρ (g/cm³) 2.4134 2.4171 2.4144 2.3956 α_(30-380° C.) (×10⁻⁷/° C.) 81.4 81.9 80.2 71.2 Ts (° C.) 915 974 963 966 10^(2.5) dPa · s (° C.) 1,574 1,653 1,636 1,635 TL ( ° C.) N.A. 1,173 1,204 1,261 logη at TL (dPa · s) N.A. 5.40 5.00 4.60 Acid resistance (HCl 5 36.0 35.9 33.8 3.9 wt % 80° C. 24 h) Alkali resistance (NaOH 0.8 0.7 0.9 1.2 5 wt % 80° C. 6 h) E (GPa) 78.4 78.0 77.1 75.6 CS_(K) (MPa) 1,160 1,195 1,171 1,128 DOL_ZERO_(K) (μm) 21.8 31.5 32.7 21.8 CS_(Na) (MPa) 351 290 303 276 DOL_ZERO_(Na) (μm) 123.7 108.7 104.6 132.6

TABLE 12 (mol %) No. 109 No. 110 No. 111 No. 112 No. 113 No. 114 SiO₂ 62.60 64.50 64.50 64.50 64.50 64.50 Al₂O₃ 18.10 18.50 18.50 18.50 18.50 18.50 B₂O₃ 0.10 0.10 0.10 0.10 0.10 0.10 Li₂O 6.33 6.00 7.00 8.00 6.00 7.00 Na₂O 8.94 6.00 5.00 4.00 7.00 6.00 K₂O 0.84 0.76 0.76 0.76 0.76 0.76 MgO 0.00 0.10 0.10 0.10 0.10 0.10 ZnO 0.00 0.00 0.00 0.00 0.00 0.00 P₂O₅ 3.05 4.00 4.00 4.00 3.00 3.00 SnO₂ 0.04 0.04 0.04 0.04 0.04 0.04 Fe₂O₃ 0.01 0.01 0.01 0.01 0.01 0.01 TiO₂ 0.00 0.00 0.00 0.00 0.00 0.00 Cl 0.01 0.01 0.01 0.01 0.01 0.01 (Na − Li)/(Al + B + P) 0.12 0.00 −0.09 −0.18 0.05 −0.05 (B + Na − P)/(Al + Li) 0.25 0.09 0.04 0.00 0.17 0.12 Si + 1.2P − 3Al − 2Li − −15.05 −8.06 −8.56 −9.06 −10.76 −11.26 1.5Na − K − B ρ (g/cm³) 2.4049 2.3812 2.3791 2.377 2.3945 2.3926 α_(30-380° C.) (×10⁻⁷/° C.) 78.7 61.7 60.2 59.5 66.8 65.2 Ts (° C.) 947 981 972 966 976 968 10^(2.5) dPa · s (° C.) 1,642 1,644 1,632 1,618 1,636 1,623 TL ( ° C.) 1,086 N.A. N.A. N.A. N.A. N.A. logη at TL (dPa · s) 5.93 N.A. N.A. N.A. N.A. N.A. Acid resistance (HCl 5 14.1 1.6 1.9 1.5 3.0 2.5 wt % 80° C. 24 h) Alkali resistance (NaOH 1.1 N.A. 1.4 N.A. N.A. N.A. 5 wt % 80° C. 6 h) E (GPa) 75.3 75.8 76.6 77.1 76.6 77.4 CS_(K) (MPa) 1,106 963 962 963 1,047 1,049 DOL_ZERO_(K) (μm) 28.9 20.5 21.1 18.6 24.2 21.9 CS_(Na) (MPa) 262 202 287 286 223 276 DOL_ZERO_(Na) (μm) 122.6 134.4 119.2 125.3 132.8 124.9 (mol %) No. 115 No. 116 No. 117 No. 118 SiO₂ 64.50 64.50 64.50 64.50 Al₂O₃ 18.50 18.50 18.50 18.50 B₂O₃ 0.10 0.10 0.10 0.10 Li₂O 8.00 6.00 7.00 8.00 Na₂O 5.00 8.00 7.00 6.00 K₂O 0.76 0.76 0.76 0.76 MgO 0.10 0.10 0.10 0.10 ZnO 0.00 0.00 0.00 0.00 P₂O₅ 3.00 2.00 2.00 2.00 SnO₂ 0.04 0.04 0.04 0.04 Fe₂O₃ 0.01 0.01 0.01 0.01 TiO₂ 0.00 0.00 0.00 0.00 Cl 0.01 0.01 0.01 0.01 (Na − Li)/(Al + B + P) −0.14 0.10 0.00 −0.10 (B + Na − P)/(Al + Li) 0.08 0.25 0.20 0.15 Si + 1.2P − 3Al − 2Li − −11.76 13.46 −13.96 −14.46 1.5Na − K − B ρ (g/cm³) 2.3908 2.4074 2.4049 2.4024 α_(30-380° C.) (×10⁻⁷/° C.) 64 71.9 70.2 69 Ts (° C.) 961 974 965 957 10^(2.5) dPa · s (° C.) 1,612 1,630 1,618 1,609 TL ( ° C.) N.A. N.A. N.A. N.A. logη at TL (dPa · s) N.A. N.A. N.A. N.A. Acid resistance (HCl 5 2.3 5.2 4.3 4.1 wt % 80° C. 24 h) Alkali resistance (NaOH N.A. N.A. 0.9 1.3 5 wt % 80° C. 6 h) E (GPa) 78.1 77.3 78.0 N.A. CS_(K) (MPa) 1,055 1,149 1,141 1,129 DOL_ZERO_(K) (μm) 18.6 24.6 22.0 20.4 CS_(Na) (MPa) 286 234 276 N.A. DOL_ZERO_(Na) (μm) 123.6 128.1 123.7 N.A.

TABLE 13 (mol %) No. 119 No. 120 No. 121 No. 122 No. 123 No. 124 No. 125 No. 126 No. 127 No. 128 SiO₂ 64.50 64.50 64.50 64.50 64.50 64.50 64.50 64.50 64.50 61.30 Al₂O₃ 18.50 18.50 18.50 18.50 18.50 18.50 18.50 18.50 18.50 15.40 B₂O₃ 0.10 0.10 0.10 0.10 0.10 0.10 0.10 0.10 0.10 0.10 Li₂O 6.38 7.38 8.38 6.38 7.38 8.38 6.38 7.38 8.38 7.80 Na₂O 6.38 5.38 4.38 7.38 6.38 5.38 8.38 7.38 6.38 7.00 K₂O 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 2.50 MgO 0.10 0.10 0.10 0.10 0.10 0.10 0.10 0.10 0.10 2.36 ZnO 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 P₂O₅ 4.00 4.00 4.00 3.00 3.00 3.00 2.00 2.00 2.00 3.50 SnO₂ 0.04 0.04 0.04 0.04 0.04 0.04 0.04 0.04 0.04 0.04 Fe₂O₃ 0.01 0.01 0.01 0.01 0.01 0.01 0.01 0.01 0.01 0.01 TiO₂ 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 Cl 0.01 0.01 0.01 0.01 0.01 0.01 0.01 0.01 0.01 0.01 (Na − Li)/(Al + B + P) 0.00 −0.09 −0.18 0.05 −0.05 −0.14 0.10 0.00 −0.10 −0.04 (B + Na − P)/(Al + Li) 0.10 0.06 0.02 0.18 0.13 0.09 0.26 0.21 0.17 0.16 Si + 1.2P − 3Al − 2Li − −8.63 −9.13 −9.63 −11.33 −11.83 −12.33 −14.03 −14.53 −15.03 −9.40 1.5Na − K − B ρ (g/cm³) N.A. N.A. N.A. N.A. N.A. N.A. N.A. N.A. N.A. 2.4176 α_(30-380° C.) (×10⁻⁷/° C.) N.A. N.A. N.A. N.A. N.A. N.A. N.A. N.A. N.A. 86.5 Ts (° C.) N.A. N.A. N.A. N.A. N.A. N.A. N.A. N.A. N.A. 883 10^(2.5) dPa · s (° C.) N.A. N.A. N.A. N.A. N.A. N.A. N.A. N.A. N.A. 1,560 TL ( ° C.) N.A. N.A. N.A. N.A. N.A. N.A. N.A. N.A. N.A. 1,034 logη at TL (dPa · s) N.A. N.A. N.A. N.A. N.A. N.A. N.A. N.A. N.A. 5.56 Acid resistance (HCl 5 N.A. N.A. N.A. N.A. N.A. N.A. N.A. N.A. N.A. 4.6 wt % 80° C. 24 h) Alkali resistance (NaOH N.A. N.A. N.A. N.A. N.A. N.A. N.A. N.A. N.A. 1.0 5 wt % 80° C. 6 h) E (GPa) N.A. N.A. N.A. N.A. N.A. N.A. N.A. N.A. N.A. 76.1 CS_(K) (MPa) N.A. N.A. N.A. N.A. N.A. N.A. N.A. N.A. N.A. 919 DOL_ZERO_(K) (μm) N.A. N.A. N.A. N.A. N.A. N.A. N.A. N.A. N.A. 35.8 CS_(Na) (MPa) N.A. N.A. N.A. N.A. N.A. N.A. N.A. N.A. N.A. 228 DOL_ZERO_(Na) (μm) N.A. N.A. N.A. N.A. N.A. N.A. N.A. N.A. N.A. 108.5

TABLE 14 (mol %) No. 129 No. 130 No. 131 No. 132 No. 133 No. 134 SiO₂ 61.00 60.20 59.80 59.80 60.50 61.00 Al₂O₃ 15.00 15.40 16.50 15.40 15.00 15.00 B₂O₃ 0.10 0.10 0.10 0.10 0.10 0.10 Li₂O 8.00 8.00 7.80 7.80 8.00 9.00 Na₂O 7.80 7.80 7.00 7.00 7.80 6.80 K₂O 1.50 1.50 2.50 2.50 1.50 1.50 MgO 2.06 2.46 3.46 2.36 2.06 2.06 ZnO 0.00 0.00 0.00 0.00 0.00 0.00 P₂O₅ 4.50 4.50 2.80 4.00 5.00 4.50 SnO₂ 0.04 0.04 0.04 0.04 0.04 0.04 Fe₂O₃ 0.01 0.01 0.01 0.01 0.01 0.01 TiO₂ 0.00 0.00 0.00 0.00 0.00 0.00 Cl 0.01 0.01 0.01 0.01 0.01 0.01 (Na − Li)/(Al + B + P) −0.01 −0.01 −0.04 −0.04 −0.01 −0.11 (B + Na − P)/(Al + Li) 0.15 0.15 0.18 0.13 0.13 0.10 Si + 1.2P − 3Al − 2Li − −7.90 −9.90 −15.04 −10.30 −7.80 −8.40 1.5Na − K − B ρ (g/cm³) 2.4098 2.4145 2.435 2.417 2.4083 2.4076 α_(30-380° C.) (×10⁻⁷/° C.) 86.2 86.5 86.3 87.4 86.4 84.6 Ts (° C.) 875 873 N.A. 879 872 870 10^(2.5) dPa · s (° C.) 1,554 1,545 1,524 1,553 1,554 1,546 TL ( ° C.) 1,022 N.A. 1,040 N.A. 1,012 1,080 logη at TL (dPa · s) 5.47 N.A. 5.53 N.A. 5.46 N.A. Acid resistance (HCl 5 2.2 4.7 38.8 5.8 2.3 1.8 wt % 80° C. 24 h) Alkali resistance (NaOH 1.2 1.1 1.0 1.3 1.3 1.0 5 wt % 80° C. 6 h) E (GPa) 75.3 N.A. 78.6 N.A. 76.7 76 CS_(K) (MPa) 878 920 1,015 916 873 912 DOL_ZERO_(K) (μm) 36.5 36.1 29.9 38.0 34.6 29.5 CS_(Na) (MPa) 223 N.A. 257 N.A. 173 283 DOL_ZERO_(Na) (μm) 123.2 N.A. 95.5 N.A. 123.5 122.0 (mol %) No. 135 No. 136 No. 137 No. 138 SiO₂ 60.50 61.00 60.50 58.46 Al₂O₃ 15.00 15.00 15.00 16.15 B₂O₃ 0.10 0.10 0.10 0.10 Li₂O 9.00 7.00 7.00 9.25 Na₂O 6.80 8.80 8.80 6.75 K₂O 1.50 1.50 1.50 0.75 MgO 2.06 2.06 2.06 4.00 ZnO 0.00 0.00 0.00 0.00 P₂O₅ 5.00 4.50 5.00 4.50 SnO₂ 0.04 0.04 0.04 0.04 Fe₂O₃ 0.01 0.01 0.01 0.01 TiO₂ 0.00 0.00 0.00 0.00 Cl 0.01 0.01 0.01 0.01 (Na − Li)/(Al + B + P) −0.11 0.09 0.09 −0.12 (B + Na − P)/(Al + Li) 0.08 0.20 0.18 0.09 Si + 1.2P − 3Al − 2Li − −8.30 −7.40 −7.30 −14.07 1.5Na − K − B ρ (g/cm³) 2.4049 2.4126 2.4109 2.4254 α_(30-380° C.) (×10⁻⁷/° C.) 84.9 88.1 88.5 80.6 Ts (° C.) 864 881 876 N.A. 10^(2.5) dPa · s (° C.) 1,543 1,566 1,565 1,492 TL ( ° C.) 1,069 992 989 1,117 logη at TL (dPa · s) N.A. N.A. N.A. 4.46 Acid resistance (HCl 5 2.1 2.2 2.4 8.9 wt % 80° C. 24 h) Alkali resistance (NaOH 1.1 1.2 1.2 1.3 5 wt % 80° C. 6 h) E (GPa) 75.4 74.5 74.1 78.3 CS_(K) (MPa) 886 923 897 1,006 DOL_ZERO_(K) (μm) 31.8 36.2 36.7 22.0 CS_(Na) (MPa) 291 228 228 338 DOL_ZERO_(Na) (μm) 119.1 117.8 111.7 116.3

TABLE 15 (mol %) No. 139 No. 140 No. 141 No. 142 No. 143 SiO₂ 61.26 68.20 68.20 61.30 60.40 Al₂O₃ 15.40 9.50 9.50 15.40 16.15 B₂O₃ 0.10 0.10 0.10 0.10 0.10 Li₂O 8.64 9.00 8.00 7.80 9.25 Na₂O 6.46 8.16 8.16 7.00 6.75 K₂O 2.50 3.00 3.00 2.50 0.75 MgO 2.40 2.00 3.00 2.36 2.06 ZnO 0.00 0.00 0.00 0.00 0.00 P₂O₅ 3.20 0.00 0.00 3.50 4.50 SnO₂ 0.04 0.04 0.04 0.04 0.04 Fe₂O₃ 0.01 0.01 0.01 0.01 0.01 TiO₂ 0.00 0.00 0.00 0.00 0.00 Cl 0.01 0.01 0.01 0.01 0.01 (Na − Li)/(Al + B + P) −0.12 −0.09 0.02 −0.04 −0.12 (B + Na − P)/(Al + Li) 0.14 0.45 0.47 0.16 0.09 Si + 1.2P − 3Al − 2Li − −10.67 6.36 8.36 −9.40 −12.13 1.5Na − K − B ρ (g/cm³) 2.4200 2.4279 2.4264 2.4181 2.4088 α_(30-380° C.) (×10⁻⁷/° C.) 87.4 94.3 95.9 87.5 79.5 Ts (° C.) N.A. 701 685 884 N.A. 10^(2.5) dPa · s (° C.) 1,537 1,427 1,435 1,556 1,534 TL ( ° C.) 1,055 879 884 N.A. N.A. logη at TL (dPa · s) 5.28 N.A. N.A. N.A. N.A. Acid resistance (HCl 5 3.9 0.0 0.0 3.8 5 .4 wt % 80° C. 24 h) Alkali resistance (NaOH 1.0 0.6 0.6 0.9 1.1 5 wt % 80° C. 6 h) E (GPa) 77.3 77.6 77.4 76.2 76.9 CS_(K) (MPa) 934 506 473 943 957 DOL_ZERO_(K) (μm) 36.5 17.3 19.8 38.3 25.9 CS_(Na) (MPa) 312 136 175 N.A. N.A. DOL_ZERO_(Na) (μm) 101.3 78.7 62.3 N.A. N.A. (mol %) No. 144 No. 145 No. 146 No. 147 No. 148 SiO₂ 68.20 70.20 61.40 60.30 60.73 Al₂O₃ 9.50 9.50 18.50 18.80 18.94 B₂O₃ 0.10 0.10 0.10 0.10 0.10 Li₂O 9.00 9.00 6.80 7.20 7.50 Na₂O 6.16 6.16 8.40 8.10 7.85 K₂O 3.00 3.00 0.30 0.45 0.30 MgO 4.00 2.00 0.50 0.50 0.50 ZnO 0.00 0.00 0.00 0.00 0.00 P₂O₅ 0.00 0.00 3.96 4.30 4.50 SnO₂ 0.04 0.04 0.04 0.16 0.16 Fe₂O₃ 0.01 0.01 0.01 0.01 0.01 TiO₂ 0.00 0.00 0.00 0.00 0.00 Cl 0.01 0.01 0.01 0.10 0.10 (Na − Li)/(Al + B + P) −0.30 −0.30 0.07 0.04 0.01 (B + Na − P)/(Al + Li) 0.34 0.34 0.18 0.15 0.13 Si + 1.2P − 3Al − 2Li − 9.36 11.36 −15.95 −18.04 −17.86 1.5Na − K − B ρ (g/cm³) 2.4239 2.4100 2.4022 2.4068 N.A. α_(30-380° C.) (×10⁻⁷/° C.) 88.8 86.7 74.9 74.8 N.A. Ts (° C.) 713 713 931 926 N.A. 10^(2.5) dPa · s (° C.) 1,445 1,479 1,596 1,579 N.A. TL ( ° C.) N.A. N.A. 1,080 1,140 N.A. logη at TL (dPa · s) N.A. N.A. 5.82 5.3 N.A. Acid resistance (HCl 5 0.0 0.0 13.5 20.7 N.A. wt % 80° C. 24 h) Alkali resistance (NaOH 0.5 0.6 1.2 1.1 N.A. 5 wt % 80° C. 6 h) E (GPa) 78.8 77.6 N.A. 75.9 N.A. CS_(K) (MPa) 561 508 1,067 1,072 N.A. DOL_ZERO_(K) (μm) 14.7 19.0 25.0 25.2 N.A. CS_(Na) (MPa) N.A. N.A. 291 260 N.A. DOL_ZERO_(Na) (μm) N.A. N.A. 132.5 125.8 N.A.

TABLE 16 (mol %) No. 149 No. 150 No. 151 No. 152 No. 153 No. 154 No. 155 No. 156 No. 157 No. 158 SiO₂ 61.02 60.55 60.73 60.43 66.16 64.12 62.82 62.35 61.84 61.42 Al₂O₃ 18.57 18.51 18.51 18.76 11.85 14.09 15.44 15.95 16.51 16.87 B₂O₃ 0.12 0.11 0.11 0.10 0.36 0.31 0.33 0.31 0.21 0.26 Li₂O 7.13 6.91 6.82 7.22 0.52 2.61 3.81 4.24 4.81 5.23 Na₂O 8.21 8.38 8.48 8.08 14.66 12.79 11.74 11.34 10.87 10.52 K₂O 0.35 0.49 0.49 0.44 1.29 1.03 0.87 0.81 0.74 0.70 MgO 0.72 0.67 0.67 0.52 4.64 3.40 2.62 2.35 2.06 1.85 ZnO 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 P₂O₅ 4.28 4.13 3.94 4.31 0.23 1.43 2.16 2.45 2.77 2.97 SnO₂ 0.16 0.16 0.16 0.05 0.15 0.12 0.09 0.09 0.08 0.08 Fe₂O₃ 0.01 0.01 0.01 0.00 0.00 0.00 0.00 0.00 0.00 0.00 TiO₂ 0.00 0.00 0.00 0.00 0.01 0.01 0.01 0.01 0.01 0.01 Cl 0.10 0.10 0.10 0.10 0.10 0.08 0.07 0.07 0.07 0.07 (Na − Li)/(Al + B + P) 0.05 0.06 0.07 0.04 1.14 0.64 0.44 0.38 0.31 0.26 (B + Na − P)/(Al + Li) 0.16 0.17 0.18 0.15 1.20 0.70 0.51 0.46 0.39 0.35 Si + 1.2P − 3Al − 2Li − −16.59 −17.02 −17.02 −17.78 6.19 −2.16 −7.33 −9.16 −11.24 −12.82 1.5Na − K − B ρ (g/cm³) 2.4068 N.A. 2.4092 N.A. 2.4483 2.439 2.4326 2.429 2.4257 2.4231 α_(30-380° C.) (×10⁻⁷/° C.) 73.5 N.A. 75.7 N.A. N.A. N.A. N.A. N.A. N.A. N.A. Ts (° C.) 923 N.A. 927 N.A. N.A. N.A. N.A. N.A. N.A. N.A. 10^(2.5) dPa · s (° C.) 1,293 N.A. 1,587 N.A. N.A. N.A. N.A. N.A. N.A. N.A. TL ( ° C.) 1,125 N.A. 1,125 N.A. N.A. N.A. N.A. N.A. N.A. N.A. logη at TL (dPa · s) 5.3 N.A. 5.3 N.A. N.A. N.A. N.A. N.A. N.A. N.A. Acid resistance (HCl 5 19.1 N.A. 20.7 N.A. N.A. N.A. N.A. N.A. N.A. N.A. wt % 80° C. 24 h) Alkali resistance (NaOH 1.3 N.A. 1.1 N.A. N.A. N.A. N.A. N.A. N.A. N.A. 5 wt % 80° C. 6 h) E (GPa) N.A. N.A. 76 N.A. N.A. N.A. N.A. N.A. N.A. N.A. CS_(K) (MPa) 1,064 N.A. 1,086 N.A. N.A. N.A. N.A. 1,164 1,151 1,138 DOL_ZERO_(K) (μm) 26.6 N.A. 23.5 N.A. N.A. N.A. N.A. 31.6 29 26.1 CS_(Na) (MPa) 271 N.A. 246 N.A. N.A. N.A. N.A. 168 198 214 DOL_ZERO_(Na) (μm) 132.0 N.A. 132.1 N.A. N.A. N.A. N.A. 92.8 89.6 90.4

TABLE 17 No. No. No. No. No. (mol %) 159 160 161 162 163 SiO₂ 61.13 60.80 60.45 60.27 60.09 Al₂O₃ 17.24 17.62 17.85 18.12 18.35 B₂O₃ 0.24 0.22 0.27 0.26 0.20 Li₂O 5.55 5.91 6.31 6.51 6.74 Na₂O 10.19 9.85 9.57 9.34 9.13 K₂O 0.66 0.62 0.59 0.56 0.53 MgO 1.65 1.44 1.29 1.16 1.04 ZnO 0.00 0.00 0.00 0.00 0.00 P₂O₅ 3.17 3.37 3.50 3.64 3.76 SnO₂ 0.07 0.07 0.06 0.06 0.06 Fe₂O₃ 0.00 0.00 0.00 0.00 0.00 TiO₂ 0.01 0.01 0.01 0.01 0.01 Cl 0.07 0.06 0.06 0.06 0.06 (Na − Li)/(Al + B + P) 0.23 0.19 0.15 0.13 0.11 (B + Na − P)/(Al + Li) 0.32 0.28 0.26 0.24 0.22 Si + 1.2P − 3Al − 2Li − −14.08 −15.46 −16.74 −17.57 −18.34 1.5Na − K − B ρ (g/cm³) 2.4203 2.4179 2.4164 2.4147 2.4132 α_(30-380° C.) (×10⁻⁷/° C.) N.A. N.A. N.A. N.A. N.A. Ts (° C.) N.A. 895 N.A. N.A. N.A. 10^(2.5) dPa · s (° C.) N.A. 1,587 N.A. N.A. N.A. TL ( ° C.) N.A. N.A. N.A. N.A. N.A. logη at TL (dPa · s) N.A. N.A. N.A. N.A. N.A. Acid resistance (HCl 5 N.A. N.A. N.A. N.A. N.A. wt % 80° C. 24 h) Alkali resistance (NaOH N.A. N.A. N.A. N.A. N.A. 5 wt % 80° C. 6 h) E (GPa) N.A. N.A. N.A. N.A. N.A. CS_(K) (MPa) 1,133 1,126 1,122 1,122 1,112 DOL_ZERO_(K) (μm) 24.8 24.1 23.4 22.8 22.3 CS_(Na) (MPa) 216 218 235 236 253 DOL_ZERO_(Na) (μm) 96.7 102.8 95 96.5 97.5 No. No. No. No. No. (mol %) 164 165 166 167 168 SiO₂ 59.88 59.76 59.64 59.64 59.63 Al₂O₃ 18.55 18.73 18.81 18.91 18.99 B₂O₃ 0.23 0.22 0.17 0.20 0.16 Li₂O 7.02 7.17 7.41 7.41 7.49 Na₂O 8.91 8.74 8.64 8.53 8.45 K₂O 0.51 0.49 0.48 0.47 0.47 MgO 0.90 0.79 0.71 0.65 0.58 ZnO 0.00 0.00 0.00 0.00 0.00 P₂O₅ 3.86 3.95 4.00 4.05 4.10 SnO₂ 0.05 0.05 0.05 0.05 0.05 Fe₂O₃ 0.00 0.00 0.00 0.00 0.00 TiO₂ 0.01 0.01 0.01 0.01 0.01 Cl 0.06 0.06 0.06 0.06 0.06 (Na − Li)/(Al + B + P) 0.08 0.07 0.05 0.05 0.04 (B + Na − P)/(Al + Li) 0.21 0.19 0.18 0.18 0.17 Si + 1.2P − 3Al − 2Li − −19.28 −19.86 −20.40 −20.51 −20.70 1.5Na − K − B ρ (g/cm³) 2.4117 2.4105 2.4097 2.4085 2.4081 α_(30-380° C.) (×10⁻⁷/° C.) N.A. N.A. N.A. N.A. N.A. Ts (° C.) N.A. N.A. N.A. N.A. N.A. 10^(2.5) dPa · s (° C.) N.A. N.A. N.A. N.A. N.A. TL ( ° C.) N.A. N.A. N.A. N.A. N.A. logη at TL (dPa · s) N.A. N.A. N.A. N.A. N.A. Acid resistance (HCl 5 N.A. N.A. N.A. N.A. N.A. wt % 80° C. 24 h) Alkali resistance (NaOH N.A. N.A. N.A. N.A. N.A. 5 wt % 80° C. 6 h) E (GPa) N.A. N.A. N.A. N.A. N.A. CS_(K) (MPa) 1,114 1,114 1,117.44 1,100 1,103 DOL_ZERO_(K) (μm) 22.4 22.3 21.4265 22.2 21.7 CS_(Na) (MPa) 259 260 249 268 273 DOL_ZERO_(Na) (μm) 101.5 98.4 107 99.7 100.7

TABLE 18 (mol %) No. 169 No. 170 No. 171 No. 172 No. 173 SiO₂ 59.52 59.57 59.69 59.77 59.89 Al₂O₃ 19.00 18.99 18.99 18.94 18.94 B₂O₃ 0.19 0.21 0.23 0.20 0.12 Li₂O 7.65 7.65 7.54 7.57 7.55 Na₂O 8.38 8.34 8.30 8.27 8.27 K₂O 0.47 0.46 0.46 0.46 0.46 MgO 0.53 0.48 0.45 0.43 0.40 ZnO 0.00 0.00 0.00 0.00 0.00 P₂O₅ 4.12 4.15 4.18 4.20 4.22 SnO₂ 0.05 0.05 0.05 0.05 0.05 Fe₂O₃ 0.00 0.00 0.00 0.00 0.00 TiO₂ 0.01 0.01 0.01 0.01 0.01 Cl 0.06 0.06 0.06 0.06 0.06 (Na − Li)/(Al + B + P) 0.03 0.03 0.03 0.03 0.03 (B + Na − P)/(Al + Li) 0.17 0.16 0.16 0.16 0.16 Si + 1.2P − 3Al − 2Li − −21.06 −20.91 −20.50 −20.23 −19.96 1.5Na − K − B ρ (g/cm³) 2.4076 2.4065 2.4055 2.4048 2.4038 α_(30-380° C.) (×10⁻⁷/° C.) N.A. N.A. N.A. N.A. N.A. Ts (° C.) N.A. 902 N.A. N.A. N.A. 10^(2.5) dPa · s (° C.) N.A. 1,577 N.A. N.A. N.A. TL ( ° C.) N.A. N.A. N.A. N.A. N.A. logη at TL (dPa · s) N.A. N.A. N.A. N.A. N.A. Acid resistance (HCl 5 N.A. 29.6 N.A. N.A. N.A. wt % 80° C. 24 h) Alkali resistance (NaOH N.A. 1.6 N.A. N.A. N.A. 5 wt % 80° C. 6 h) E (GPa) N.A. N.A. N.A. N.A. N.A. CS_(K) (MPa) 1,103 1,102 1,108 1,108 1,108 DOL_ZERO_(K) (μm) 21.3 21.3 22 23.4 23.6 CS_(Na) (MPa) 274 264 276 258 251 DOL_ZERO_(Na) (μm) 94.9 100.5 106.5 106.7 91.2 (mol %) No. 174 No. 175 No. 176 No. 177 No. 178 SiO₂ 59.97 59.86 59.91 59.97 60.13 Al₂O₃ 18.97 18.97 18.98 18.93 18.91 B₂O₃ 0.10 0.13 0.18 0.19 0.18 Li₂O 7.51 7.66 7.57 7.53 7.42 Na₂O 8.24 8.22 8.21 8.22 8.20 K₂O 0.45 0.45 0.45 0.45 0.45 MgO 0.37 0.33 0.31 0.34 0.32 ZnO 0.00 0.00 0.00 0.00 0.00 P₂O₅ 4.24 4.24 4.23 4.22 4.24 SnO₂ 0.05 0.05 0.04 0.05 0.04 Fe₂O₃ 0.00 0.00 0.00 0.00 0.00 TiO₂ 0.01 0.01 0.01 0.01 .01 Cl 0.06 0.06 0.07 0.06 0.07 (Na − Li)/(Al + B + P) 0.03 0.02 0.03 0.03 0.03 (B + Na − P)/(Al + Li) 0.15 0.15 0.16 0.16 0.16 Si + 1.2P − 3Al − 2Li − −19.80 −20.17 −20.04 −19.78 −19.28 1.5Na − K − B ρ (g/cm³) 2.4034 2.4029 2.4027 2.4029 2.4016 α_(30-380° C.) (×10⁻⁷/° C.) N.A. N.A. N.A. N.A. N.A. Ts (° C.) N.A. N.A. N.A. 907 N.A. 10^(2.5) dPa · s (° C.) N.A. N.A. N.A. 1,577 N.A. TL ( ° C.) N.A. N.A. N.A. N.A. N.A. logη at TL (dPa · s) N.A. N.A. N.A. N.A. N.A. Acid resistance (HCl 5 N.A. N.A. N.A. 21.6 N.A. wt % 80° C. 24 h) Alkali resistance (NaOH N.A. N.A. N.A. 1.6 N.A. 5 wt % 80° C. 6 h) E (GPa) N.A. N.A. N.A. N.A. N.A. CS_(K) (MPa) 1,112 1,104 1,109 1,108 N.A. DOL_ZERO_(K) (μm) 23.7 23.5 23.3 24.4 N.A. CS_(Na) (MPa) 262 271 269 264 N.A. DOL_ZERO_(Na) (μm) 101.7 98.4 106.3 99.6 N.A.

TABLE 19 (mol %) No. 179 No. 180 No. 181 No. 182 No. 183 No. 184 SiO₂ 60.16 60.18 60.28 60.15 60.20 60.14 Al₂O₃ 18.92 18.91 18.95 18.93 18.95 18.95 B₂O₃ 0.19 0.22 0.20 0.22 0.17 0.18 Li₂O 7.38 7.37 7.22 7.40 7.39 7.45 Na₂O 8.18 8.18 8.20 8.17 8.17 8.17 K₂O 0.45 0.44 0.44 0.44 0.43 0.43 MgO 0.29 0.27 0.26 0.23 0.22 0.20 ZnO 0.00 0.00 0.00 0.00 0.00 0.00 P₂O₅ 4.27 4.27 4.28 4.29 4.30 4.30 SnO₂ 0.04 0.04 0.05 0.05 0.05 0.05 Fe₂O₃ 0.00 0.00 0.00 0.00 0.00 0.00 TiO₂ 0.01 0.01 0.01 0.01 0.01 0.01 Cl 0.07 0.07 0.07 0.08 0.08 0.08 (Na − Li)/(Al + B + P) 0.03 0.03 0.04 0.03 0.03 0.03 (B + Na − P)/(Al + Li) 0.16 0.16 0.16 0.16 0.15 0.15 Si + 1.2P − 3Al − 2Li − −19.14 −19.09 −18.83 −19.22 −19.12 −19.32 1.5Na − K − B ρ (g/cm³) 2.4017 2.4015 2.4011 N.A. N.A. 2.4005 α_(30-380° C.) (×10⁻⁷/° C.) N.A. N.A. N.A. N.A. N.A. N.A. Ts (° C.) N.A. N.A. 908 N.A. N.A. N.A. 10^(2.5) dPa · s (° C.) N.A. N.A. 1,575 N.A. N.A. N.A. TL ( ° C.) N.A. N.A. N.A. N.A. N.A. N.A. logη at TL (dPa · s) N.A. N.A. N.A. N.A. N.A. N.A. Acid resistance (HCl 5 N.A. N.A. 19.9 N.A. N.A. N.A. wt % 80° C. 24 h) Alkali resistance (NaOH N.A. N.A. 1.5 N.A. N.A. N.A. 5 wt % 80° C. 6 h) E (GPa) N.A. N.A. N.A. N.A. N.A. N.A. CS_(K) (MPa) N.A. 1,101 1,094 1,100 1,093 1,096 DOL_ZERO_(K) (μm) N.A. 24.8 24.5 23.6 24.3 23.7 CS_(Na) (MPa) N.A. 272 269 249 246 244 DOL_ZERO_(Na) (μm) N.A. 110.8 103.2 111.7 103.1 105 (mol %) No. 185 No. 186 No. 187 No. 188 SiO₂ 60.38 60.38 60.38 60.28 Al₂O₃ 18.57 18.57 18.57 18.67 B₂O₃ 0.10 0.10 0.10 0.10 Li₂O 7.13 7.63 7.13 7.13 Na₂O 8.21 8.21 8.21 8.21 K₂O 0.35 0.35 0.85 0.35 MgO 0.72 0.72 0.72 0.72 ZnO 0.00 0.00 0.00 0.00 P₂O₅ 4.28 3.78 3.78 4.28 SnO₂ 0.16 0.16 0.16 0.16 Fe₂O₃ 0.00 0.00 0.00 0.00 TiO₂ 0.00 0.00 0.00 0.00 Cl 0.10 0.10 0.10 0.10 (Na − Li)/(Al + B + P) 0.05 0.03 0.05 0.05 (B + Na − P)/(Al + Li) 0.16 0.17 0.18 0.16 Si + 1.2P − 3Al − 2Li − −17.22 −18.82 −18.32 −17.62 1.5Na − K − B ρ (g/cm³) 2.4068 2.4114 2.4128 2.4076 α_(30-380° C.) (×10⁻⁷/° C.) 73.5 75.7 76.8 75.1 Ts (° C.) 923 919 919 920 10^(2.5) dPa · s (° C.) 1,580 1,566 1,574 1,573 TL ( ° C.) 1,125 1,113 1,167 1,136 logη at TL (dPa · s) 5.3 5.3 4.9 5.2 Acid resistance (HCl 5 19.1 30.4 33.5 20.6 wt % 80° C. 24 h) Alkali resistance (NaOH 1.3 1.3 1.3 1.4 5 wt % 80° C. 6 h) E (GPa) N.A. N.A. N.A. N.A. CS_(K) (MPa) 1,064 1,086 1,067 1,055 DOL_ZERO_(K) (μm) 27 23 28 25 CS_(Na) (MPa) 271 294 263 253 DOL_ZERO_(Na) (μm) 132 127 131 129

TABLE 20 (mol %) No. 189 No. 190 No. 191 No. 192 No. 193 No. 194 SiO₂ 60.28 60.28 59.88 59.88 59.78 59.78 Al₂O₃ 18.67 18.67 18.57 18.57 18.67 18.67 B₂O₃ 0.10 0.10 0.10 0.10 0.10 0.10 Li₂O 7.63 7.13 7.63 7.13 7.63 7.13 Na₂O 8.21 8.21 8.21 8.21 8.21 8.21 K₂O 0.35 0.85 0.35 0.85 0.35 0.85 MgO 0.72 0.72 0.72 0.72 0.72 0.72 ZnO 0.00 0.00 0.00 0.00 0.00 0.00 P₂O₅ 3.78 3.78 4.28 4.28 4.28 4.28 SnO₂ 0.16 0.16 0.16 0.16 0.16 0.16 Fe₂O₃ 0.00 0.00 0.00 0.00 0.00 0.00 TiO₂ 0.00 0.00 0.00 0.00 0.00 0.00 Cl 0.10 0.10 0.10 0.10 0.10 0.10 (Na − Li)/(Al + B + P) 0.03 0.05 0.03 0.05 0.03 0.05 (B + Na − P)/(Al + Li) 0.17 0.18 0.15 0.16 0.15 0.16 Si + 1.2P − 3Al − 2Li − −19.22 −18.72 −18.72 −18.22 −19.12 −18.62 1.5Na − K − B ρ (g/cm³) 2.4124 2.4133 2.4095 2.41 2.4096 2.4107 α_(30-380° C.) (×10⁻⁷/° C.) 75.1 77.5 76.1 77.7 76.2 76.4 Ts (° C.) 915 919 910 913 910 914 10^(2.5) dPa · s (° C.) 1,564 1,574 1,567 1,575 1,565 1,574 TL ( ° C.) 1,166 1,166 1,160 1,155 1,155 1,146 logη at TL (dPa · s) 4.8 4.9 4.9 5.0 4.9 5.0 Acid resistance (HCl 5 34.5 38.1 28.4 31 30.2 31.5 wt % 80° C. 24 h) Alkali resistance (NaOH 1.1 1.2 1.2 1.2 1.2 1.1 5 wt % 80° C. 6 h) E (GPa) N.A. N.A. N.A. N.A. N.A. N.A. CS_(K) (MPa) 1,088 1,071 1,062 1,038 1,054 1,044 DOL_ZERO_(K) (μm) 23 24 24 27 23 27 CS_(Na) (MPa) 265 260 265 257 297 268 DOL_ZERO_(Na) (μm) 140 131 134 130 129 129 (mol %) No. 195 No. 196 No. 197 No. 198 SiO₂ 60.33 60.36 60.38 63.42 Al₂O₃ 18.80 18.80 18.80 15.12 B₂O₃ 0.10 0.10 0.10 0.28 Li₂O 7.20 7.20 7.20 3.61 Na₂O 8.10 8.10 8.10 11.63 K₂O 0.45 0.45 0.45 0.91 MgO 0.50 0.50 0.50 2.66 ZnO 0.00 0.00 0.00 0.00 P₂O₅ 4.30 4.30 4.30 2.15 SnO₂ 0.12 0.09 0.07 0.11 Fe₂O₃ 0.00 0.00 0.00 0.00 TiO₂ 0.00 0.00 0.00 0.00 Cl 0.10 0.10 0.10 0.10 (Na − Li)/(Al + B + P) 0.04 0.04 0.04 0.46 (B + Na − P)/(Al + Li) 0.15 0.15 0.15 0.52 Si + 1.2P − 3Al − 2Li − −18.01 −17.98 −17.96 −5.23 1.5Na − K − B ρ (g/cm³) 2.4052 2.4046 2.4036 2.4299 α_(30-380° C.) (×10⁻⁷/° C.) N.A. N.A. N.A. N.A. Ts (° C.) N.A. N.A. N.A. N.A. 10^(2.5) dPa · s (° C.) N.A. N.A. N.A. N.A. TL ( ° C.) 1,167 1,149 1,108 1,063 logη at TL (dPa · s) 4.9 5.1 5.5 N.A. Acid resistance (HCl 5 N.A. N.A. N.A. N.A. wt % 80° C. 24 h) Alkali resistance (NaOH N.A. N.A. N.A. N.A. 5 wt % 80° C. 6 h) E (GPa) N.A. N.A. N.A. N.A. CS_(K) (MPa) N.A. 1,112 N.A. N.A. DOL_ZERO_(K) (μm) N.A. 23.3 N.A. N.A. CS_(Na) (MPa) N.A. 256 N.A. N.A. DOL_ZERO_(Na) (μm) N.A. 106.6 N.A. N.A.

TABLE 21 (mol %) No. 199 No. 200 No. 201 No. 202 No. 203 No. 204 SiO₂ 60.41 60.37 60.37 65.32 65.60 65.89 Al₂O₃ 18.80 18.80 18.80 12.83 12.48 12.13 B₂O₃ 0.10 0.10 0.10 0.40 0.41 0.43 Li₂O 7.20 7.20 7.20 1.38 1.04 0.70 Na₂O 8.10 8.10 8.10 13.83 14.17 14.50 K₂O 0.45 0.45 0.45 1.20 1.24 1.29 MgO 0.50 0.50 0.50 4.01 4.22 4.42 ZnO 0.00 0.00 0.00 0.00 0.00 0.00 P₂O₅ 4.30 4.30 4.30 0.81 0.61 0.40 SnO₂ 0.04 0.08 0.08 0.13 0.14 0.14 Fe₂O₃ 0.00 0.00 0.00 0.002 0.002 0.002 TiO₂ 0.00 0.00 0.00 0.002 0.002 0.002 Cl 0.10 0.10 0.10 0.09 0.09 0.09 (Na − Li)/(Al + B + P) 0.04 0.04 0.04 0.89 0.97 1.06 (B + Na − P)/(Al + Li) 0.15 0.15 0.15 0.94 1.03 1.13 Si + 1.2P − 3Al − 2Li − −17.93 −17.97 −17.97 2.71 3.92 5.12 1.5Na − K − B ρ (g/cm³) 2.403 2.4033 2.4031 2.4443 2.444 2.4452 α_(30-380° C.) (×10⁻⁷/° C.) 74.8 74.2 N.A. 89.4 90.5 90 Ts (° C.) 926 924 N.A. 871 870 867 10^(2.5) dPa · s (° C.) 1,569 1,579 N.A. 1,608 1,605 1,600 TL ( ° C.) 1,108 N.A. N.A. N.A. N.A. N.A. logη at TL (dPa · s) 5.5 N.A. N.A. N.A. N.A. N.A. Acid resistance (HCl 5 N.A. N.A. N.A. N.A. N.A. N.A. wt % 80° C. 24 h) Alkali resistance (NaOH N.A. N.A. N.A. N.A. N.A. N.A. 5 wt % 80° C. 6 h) E (GPa) N.A. N.A. N.A. N.A. N.A. N.A. CS_(K) (MPa) 1,130 1,109 1,107 N.A. N.A. N.A. DOL_ZERO_(K) (μm) 24.0 23.1 22.7 N.A. N.A. N.A. CS_(Na) (MPa) 245 238 244 N.A. N.A. N.A. DOL_ZERO_(Na) (μm) 110.0 111.3 109.1 N.A. N.A. N.A. (mol %) No. 205 No. 206 No. 207 No. 208 SiO₂ 66.17 59.40 59.40 59.40 Al₂O₃ 11.79 18.80 18.80 18.80 B₂O₃ 0.45 0.20 0.20 0.20 Li₂O 0.36 7.20 7.20 8.11 Na₂O 14.83 9.01 9.01 8.10 K₂O 1.33 0.45 0.45 0.45 MgO 4.62 0.50 0.02 0.50 ZnO 0.00 0.00 0.00 0.00 P₂O₅ 0.20 4.30 4.78 4.30 SnO₂ 0.15 0.04 0.04 0.04 Fe₂O₃ 0.002 0.010 0.010 0.010 TiO₂ 0.002 0.010 0.010 0.010 Cl 0.09 0.01 0.01 0.01 (Na − Li)/(Al + B + P) 1.16 0.08 0.08 0.00 (B + Na − P)/(Al + Li) 1.24 0.19 0.17 0.15 Si + 1.2P − 3Al − 2Li − 6.31 −20.41 −19.83 −20.86 1.5Na − K − B ρ (g/cm³) 2.4459 2.4084 2.4014 2.4065 α_(30-380° C.) (×10⁻⁷/° C.) 90.4 78.8 79.4 77.2 Ts (° C.) 867 909 912 901.5 10^(2.5) dPa · s (° C.) 1,597 1,563 1,572 1,555 TL ( ° C.) N.A. 1,094 1,078 1,117 logη at TL (dPa · s) N.A. 5.4 5.7 5.2 Acid resistance (HCl 5 N.A. 38.4 32.8 37.6 wt % 80° C. 24 h) Alkali resistance (NaOH N.A. 1.2 1.4 1.3 5 wt % 80° C. 6 h) E (GPa) N.A. 75.2 74.4 76.0 CS_(K) (MPa) N.A. 1,123 1,059 1,098 DOL_ZERO_(K) (μm) N.A. 27.5 30.8 25.7 CS_(Na) (MPa) N.A. 275 260 286 DOL_ZERO_(Na) (μm) N.A. 123.4 128.9 124.1

TABLE 22 (mol %) No. 209 No. 210 No. 211 No. 212 No. 213 No. 214 No. 215 SiO₂ 59.40 59.61 59.41 59.61 59.61 59.41 59.40 Al₂O₃ 18.80 18.60 18.60 18.60 18.60 18.60 18.56 B₂O₃ 0.20 0.20 0.20 0.20 0.50 0.20 0.20 Li₂O 8.11 8.11 8.11 8.11 8.11 8.11 8.11 Na₂O 8.10 8.10 8.30 8.10 8.10 8.30 8.35 K₂O 0.45 0.45 0.45 0.15 0.15 0.15 0.45 MgO 0.02 0.50 0.50 0.50 0.50 0.50 0.02 ZnO 0.00 0.00 0.00 0.00 0.00 0.30 0.00 P₂O₅ 4.78 4.30 4.30 4.60 4.30 4.30 4.78 SnO₂ 0.04 0.03 0.03 0.03 0.03 0.03 0.03 Fe₂O₃ 0.010 0.010 0.010 0.010 0.010 0.010 0.010 TiO₂ 0.010 0.010 0.010 0.010 0.010 0.010 0.010 Cl 0.01 0.01 0.01 0.01 0.01 0.01 0.01 (Na − Li)/(Al + B + P) 0.00 0.00 0.01 0.00 0.00 0.01 0.01 (B + Na − P)/(Al + Li) 0.13 0.15 0.16 0.14 0.16 0.16 0.14 Si + 1.2P − 3Al − 2Li − −20.28 −20.05 −20.55 −19.39 −20.05 −20.25 −19.94 1.5Na − K − B ρ (g/cm³) 2.3997 2.4043 2.4059 2.4018 2.4014 2.4111 2.399 α_(30-380° C.) (×10⁻⁷/° C.) 77.5 76.7 78.1 75.6 74.9 76.5 78.6 Ts (° C.) 908 N.A. N.A. N.A. N.A. N.A. N.A. 10^(2.5) dPa · s (° C.) 1,562 N.A. N.A. N.A. N.A. N.A. N.A. TL ( ° C.) 1,120 N.A. N.A. 1,090 1,092 1,130 1,098 logη at TL (dPa · s) 5.1 N.A. N.A. N.A. N.A. N.A. N.A. Acid resistance (HCl 5 29.3 31 35.8 23.6 27.2 35.2 25.5 wt % 80° C. 24 h) Alkali resistance (NaOH 1.3 N.A. N.A. N.A. N.A. N.A. N.A. 5 wt % 80° C. 6 h) E (GPa) 75.0 75.4 75 N.A. N.A. N.A. N.A. CS_(K) (MPa) 1,044 1,108 1,109 1,087 1,104 1,120 1,044 DOL_ZERO_(K) (μm) 29.3 26.8 26.7 25.3 24.2 23.8 29.9 CS_(Na) (MPa) 291 290 281 296 286 299 226 DOL_ZERO_(Na) (μm) 130.1 124.3 132.9 134.3 126.1 120.9 153

Samples in the tables were each produced as described below. First, glass raw materials were blended so as to give a glass composition shown in the table, and were melted at 1,600° C. for 21 hours in a platinum pot. Subsequently, the resultant molten glass was poured out on a carbon sheet and formed into a flat sheet shape, followed by being cooled in a temperature region of from an annealing point to a strain point at a rate of 3° C./min. Thus, a glass sheet (glass sheet to be tempered) was obtained. The surface of the resultant glass sheet was optically polished so as to give a sheet thickness of 1.5 mm, and then the glass sheet was evaluated for various characteristics.

The density (ρ) is a value measured by a well-known Archimedes method.

The thermal expansion coefficient (α_(30-380° C.)) at from 30° C. to 380° C. is a value for an average thermal expansion coefficient measured with a dilatometer.

The temperature (10 ^(2.5) dPa·s) at a viscosity at high temperature of 10^(2.5) dPa·s is a value measured by a platinum sphere pull up method.

The softening point (Ts) is a value measured based on a method of ASTM C338.

The liquidus temperature (TL) was determined as a temperature obtained as described below. Glass powder which had passed through a standard 30-mesh sieve (500 μm) and remained on a 50-mesh sieve (300 μm) was loaded into a platinum boat, and the platinum boat was kept for 24 hours in a temperature gradient furnace and was then taken out of the furnace. At this time, a highest temperature at which devitrification (devitrified stones) was observed with a microscope in glass was measured. The liquidus viscosity (log η at TL) is a value for a viscosity at the liquidus temperature measured by a platinum sphere pull up method, and is logarithmically represented as log η.

The Young's modulus (E) is a value calculated by a method in conformity with JIS R1602-1995 “Testing methods for elastic modulus of fine ceramics.”

The acid resistance test is evaluated as described below. A glass sample having been subjected to mirror polishing treatment on both sides so as to give dimensions of 50 mm×10 mm×1.0 mm was used as a measurement sample. The sample was sufficiently washed with a neutral detergent and pure water, and was then immersed in a 5 mass % HCl aqueous solution warmed to 80° C. for 24 hours. A mass loss (mg/cm²) per unit surface area before and after the immersion was calculated.

The alkali resistance test is evaluated as described below. A glass sample having been subjected to mirror polishing treatment on both sides so as to give dimensions of 50 mm×10 mm×1.0 mm was used as a measurement sample. The sample was sufficiently washed with a neutral detergent and pure water, and was then immersed in a 5 mass % NaOH aqueous solution warmed to 80° C. for 6 hours. A mass loss (mg/cm²) per unit surf ace area before and after the immersion was calculated.

Subsequently, each of the glass sheets was subjected to ion exchange treatment by being immersed in a KNO₃ molten salt at 430° C. for 4 hours. Thus, a tempered glass sheet having a compressive stress layer in a surface thereof was obtained. After that, the glass surface was washed, and the compressive stress value (CS_(K)) and the depth of layer (DOL_ZERO_(K)) of the compressive stress layer on the outermost surface were calculated based on the number of interference fringes observed with a surface stress meter FSM-6000 (manufactured by Orihara Industrial Co., Ltd.) and intervals therebetween. Herein, the “DOL_ZERO_(K)” is a depth at which the compressive stress value becomes zero. In calculation of the stress characteristics, the refractive index and the optical elastic constant of each sample were set to 1.51 and 30.1 [(nm/cm)/MPa], respectively.

In addition, each of the glass sheets was subjected to ion exchange treatment by being immersed in a NaNO₃ molten salt at 380° C. for 1 hour. Thus, a tempered glass sheet was obtained. After that, the glass surface was washed, and the compressive stress value (CS_(Na)) and the depth of layer (DOL_ZERO_(Na)) of the compressive stress layer on the outermost surface were calculated based on a phase difference distribution curve observed with a scattered light photoelastic stress meter SLP-1000 (manufactured by Orihara Industrial Co., Ltd.). Herein, the “DOL_ZERO_(Na)” is a depth at which the stress value becomes zero. In calculation of the stress characteristics, the refractive index and the optical elastic constant of each sample were set to 1.51 and 30.1 [(nm/cm)/MPa], respectively.

As apparent from the tables, it is conceived that each of Sample Nos. 1 to 35 and 38 to 215, which has a compressive stress value (CS_(K)) of the compressive stress layer on the outermost surface of 473 MPa or more when having been subjected to the ion exchange treatment with the KNO₃ molten salt, and has a compressive stress value (CS_(Na)) of the compressive stress layer on the outermost surface of 165 MPa or more when having been subjected to the ion exchange treatment with the NaNO₃ molten salt, can be subjected to ion exchange treatment with any of these molten salts, and is hardly broken at the time of dropping. Further, it is conceived that each of Sample Nos. 1 to 35 and 38 to 215, which has a liquidus viscosity of 10^(3.74) dPa·s or more, can be formed into a sheet shape. Meanwhile, it is conceived that Sample No. 36, which has a compressive stress value (CS_(Na)) of the compressive stress layer of 163 MPa, is liable to be broken at the time of dropping. In addition, it is conceived that Sample No. 37, which has a liquidus viscosity of less than 10^(3.5) dPa·s, is difficult to form into a sheet shape.

Moreover, as apparent from Tables 5 to 22, it is conceived that each of Sample Nos. 37 to 215, which has a value for the ([SiO₂]+1.2×[P₂O₅]−3×[Al₂O₃]−2×[Li₂O]−1.5×[Na₂O]−[K₂O]−[B₂O₃]) of −36 mol % or more, has high acid resistance and is therefore easily applied to an acid treatment step, and is thus suitable as a cover glass.

Example 2

First, glass raw materials were blended so as to give glass compositions of Sample No. 2 shown in Table 1 and Sample No. 35 shown in Table 4, and were melted at 1,600° C. for 21 hours in a platinum pot. Subsequently, the resultant molten glass was poured out on a carbon sheet and formed into a flat sheet shape, followed by being cooled in a temperature region of from an annealing point to a strain point at a rate of 3° C./min. Thus, a glass sheet (glass sheet to be tempered) was obtained. The surface of the resultant glass sheet was optically polished so as to give a sheet thickness of 0.7 mm for No. 2, and a sheet thickness of 0.8 mm for No. 35.

The resultant glass sheet to be tempered was subjected to ion exchange treatment by being immersed in a NaNO₃ molten salt (concentration of NaNO₃: 100 mass %) at 380° C. for 3 hours, and was then subjected to ion exchange treatment by being immersed in a mixed molten salt of KNO₃ and LiNO₃ (concentration of LiNO₃: 2.5 mass %) at 380° C. for 75 minutes. Further, the surface of the resultant tempered glass sheet was washed, and then the stress profile of the tempered glass sheet was measured with a scattered light photoelastic stress meter SLP-1000 (manufactured by Orihara Industrial Co., Ltd.) and a surface stress meter FSM-6000 (manufactured by Orihara Industrial Co., Ltd.). As a result, the same non-monotonic stress profile as in FIG. 1 , that is, a stress profile having a first peak, a second peak, a first bottom, and a second bottom was obtained in each case.

Example 3

First, glass raw materials were blended so as to give glass compositions of Sample No. 109 shown in Table 12 and Sample No. 146 shown in Table 15, and were melted at 1,600° C. for 21 hours in a platinum pot. Subsequently, the resultant molten glass was poured out on a carbon sheet and formed into a flat sheet shape, followed by being cooled in a temperature region of from an annealing point to a strain point at a rate of 3° C./min. Thus, a glass sheet (glass sheet to be tempered) was obtained. The surface of the resultant glass sheet was optically polished so as to give a sheet thickness of 0.7 mm.

The resultant glass sheet to be tempered was subjected to ion exchange treatment by being immersed in a NaNO₃ molten salt (concentration of NaNO₃: 100 mass %) at 380° C. for 3 hours, and was then subjected to ion exchange treatment by being immersed in a mixed molten salt of KNO₃ and LiNO₃ (concentration of LiNO₃: 1.5 mass %) at 380° C. for 45 minutes. Further, the surface of the resultant tempered glass sheet was washed, and then the stress profile of the tempered glass sheet was measured with a scattered light photoelastic stress meter SLP-1000 (manufactured by Orihara Industrial Co., Ltd.) and a surface stress meter FSM-6000 (manufactured by Orihara Industrial Co., Ltd.). As a result, the same non-monotonic stress profile as in FIG. 2 , that is, a stress profile having a first peak, a second peak, a first bottom, and a second bottom was obtained in each case. Accordingly, it is expected that the resultant tempered glass sheet has a low breakage probability at the time of dropping.

Example 4

First, glass raw materials were blended so as to give a glass composition of Sample No. 147 shown in Table 15, and were melted at 1,600° C. for 21 hours in a platinum pot. Subsequently, the resultant molten glass was poured out on a carbon sheet and formed into a flat sheet shape, followed by being cooled in a temperature region of from an annealing point to a strain point at a rate of 3° C./min. Thus, a glass sheet (glass sheet to be tempered) was obtained. The surface of the resultant glass sheet was optically polished so as to give a sheet thickness of 0.7 mm.

The resultant glass sheet to be tempered was subjected to ion exchange treatment by being immersed in a NaNO₃ molten salt (concentration of NaNO₃: 100 mass %) at 380° C. for 3 hours, and was then subjected to ion exchange treatment by being immersed in a mixed molten salt of KNO₃ and LiNO₃ (concentration of LiNO₃: 1.5 mass %) at 380° C. for 45 minutes. Further, the surface of the resultant tempered glass sheet was washed, and then the stress profile of the tempered glass sheet was measured with a scattered light photoelastic stress meter SLP-1000 (manufactured by Orihara Industrial Co., Ltd.) and a surface stress meter FSM-6000 (manufactured by Orihara Industrial Co., Ltd.). As a result, the same non-monotonic stress profile as in FIG. 2 , that is, a stress profile having a first peak, a second peak, a first bottom, and a second bottom was obtained in each case. Accordingly, it is expected that the resultant tempered glass sheet has a low breakage probability at the time of dropping.

INDUSTRIAL APPLICABILITY

The tempered glass sheet of the present invention is suitable as a cover glass for a touch panel display of a cellular phone, a digital camera, a personal digital assistant (PDA), or the like. In addition, the tempered glass sheet of the present invention is expected to be applied to applications for which high mechanical strength is required, for example, a window glass, a substrate for a magnetic disk, a substrate for a flat panel display, a substrate for a flexible display, a cover glass for a solar cell, a cover glass for a solid state image sensor, and a cover glass for an automobile, in addition to the above-mentioned applications. 

1-19. (canceled)
 20. A tempered glass sheet having a compressive stress layer in a surface thereof, the tempered glass sheet comprising as a glass composition, in terms of mol %, 50% to 80% of SiO₂, 8% to 25% of Al₂O₃, 0% to 10% of B₂O₃, 3% to 10% of Li₂O, 3% to 21% of Na₂O, 0% to 10% of K₂O, 10% to 18% of [Li₂O]+[Na₂O]+[K₂O], 0% to 10% of MgO, 0% to 10% of ZnO, and 0.1 to 15% of P₂O₅.
 21. The tempered glass sheet according to claim 20, wherein the tempered glass sheet has a content of Li₂O of from 3 mol % to 7 mol %.
 22. The tempered glass sheet according to claim 20, wherein the tempered glass sheet has a content of [Li₂O]+[Na₂O]+[K₂O] of from 10 mol % to 16.99 mol %.
 23. The tempered glass sheet according to claim 20, wherein the tempered glass sheet has a content of Al₂O₃ of from 16.25 mol % to 25 mol %.
 24. The tempered glass sheet according to claim 20, wherein the tempered glass sheet satisfies the following relationship: a molar ratio ([Na₂O]−[Li₂O])/([Al₂O₃]+[B₂O₃]+[P₂O₅])≤0.23.
 25. The tempered glass sheet according to claim 20, wherein the tempered glass sheet has a liquidus viscosity of 10^(3.74) dPa·s or more.
 26. The tempered glass sheet according to claim 20, wherein the compressive stress layer has a depth of layer of 140 μm or more.
 27. The tempered glass sheet according to claim 20, wherein the compressive stress layer has a compressive stress value of 900 MPa or more on an outermost surface.
 28. A glass sheet to be tempered, comprising as a glass composition, in terms of mol %, 50% to 80% of SiO₂, 8% to 25% of Al₂O₃, 0% to 10% of B₂O₃, 3% to 10% of Li₂O, 3% to 21% of Na₂O, 0% to 10% of K₂O, 10% to 18% of [Li₂O]+[Na₂O]+[K₂O], 0% to 10% of MgO, 0% to 10% of ZnO, and 0.1% to 15% of P₂O₅.
 29. The tempered glass sheet according to claim 21, wherein the tempered glass sheet has a content of [Li₂O]+[Na₂O]+[K₂O] of from 10 mol % to 16.99 mol %.
 30. The tempered glass sheet according to claim 21, wherein the tempered glass sheet has a content of Al₂O₃ of from 16.25 mol % to 25 mol %.
 31. The tempered glass sheet according to claim 21, wherein the tempered glass sheet satisfies the following relationship: a molar ratio ([Na₂O]−[Li₂O])/([Al₂O₃]+[B₂O₃]+[P₂O₅])≤0.23.
 32. The tempered glass sheet according to claim 21, wherein the tempered glass sheet has a liquidus viscosity of 10^(3.74) dPa·s or more.
 33. The tempered glass sheet according to claim 21, wherein the compressive stress layer has a depth of layer of 140 μm or more.
 34. The tempered glass sheet according to claim 21, wherein the compressive stress layer has a compressive stress value of 900 MPa or more on an outermost surface. 